JP2018005210A - Electrochromic display element, manufacturing method therefor, display device, information device, and electrochromic dimming lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic display element which can be driven at low voltage, does not exhibit coloring deterioration after being repeatedly driven, and offers good display quality.SOLUTION: An electrochromic display element comprises two electrodes 3, 4, an electrochromic layer 6 disposed between the two electrodes, and an electrolyte layer 5 located between the two electrodes. The electrochromic layer comprises a porous structure made of an electrochromic compound that gets colored by oxidation reaction.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrochromic display element, a manufacturing method thereof, a display device, an information device, and an electrochromic light control lens.

In recent years, so-called electronic paper has been actively developed as an information medium replacing paper. Display elements used for electronic paper include display elements using reflective liquid crystals, display elements using electrophoresis, display elements using toner migration, display elements using electrochromic compounds (electrochromic display elements), and the like. Is mentioned.
The electrochromic display element is a promising candidate for the next generation display element because it has a memory effect and can be driven at a low voltage, and is now an electrochromic display element from material development to device design. A wide range of research and development has been conducted.
The electrochromism phenomenon is a reversible phenomenon in which, when a voltage is applied to the electrochromic compound, the electrochromic compound causes an oxidation-reduction reaction to develop or decolor. The electrochromic display element can generate various types of colors by changing the structure of the electrochromic compound and utilizing the electrochromism phenomenon.

  For this reason, the electrochromic display element is also expected as a display element capable of multicolor display, and various proposals have been made (for example, see Patent Documents 1 to 4).

  On the other hand, in addition to the above-described electronic paper, electrochromic display elements are also being studied for application to light control elements such as light control lenses, light control windows, and antiglare mirrors. For example, an electrochromic dimming lens has been proposed in which a thin-film dimming function is laminated on a single lens, which can be thin and lightweight, and is low in cost and excellent in productivity (see Patent Document 5).

In the transmissive light control element such as the light control lens described above, high transparency as an element is an indispensable and important element for obtaining high display quality. In addition, in a reflective display element such as electronic paper, it is important for obtaining high display quality as an element that the constituent elements excluding the reflective layer have high transparency.
One factor that impairs the transparency of the electrochromic display element is deterioration coloring due to repeated driving of coloring / decoloring.
The electrochromic display element may be colored with a yellowish brown hue as a result when one or more elements constituting the element deteriorate due to repeated driving of coloring / decoloring many times. The original transparency of the decolored state is lost, and the display quality as an element is impaired. It was found that the degree of deterioration depends on the magnitude of the load applied to the element due to driving, and that the higher the applied voltage, the easier the deterioration.

  It is an object of the present invention to provide an electrochromic display element that can be driven at a lower voltage and has good display quality that does not cause deterioration coloring even when it is repeatedly driven.

In order to obtain an electrochromic display element having good display quality that does not cause deterioration coloring even if it is repeatedly driven, the inventors need to be able to be driven at a lower voltage, and for that purpose, it is a charge carrier. Ions are likely to move through each component of the element, particularly in a layer that develops color due to an oxidation reaction, and it is necessary to have a large contact area between the layer that develops color due to an oxidation reaction and ions, leading to the present invention. .
The electrochromic display element of the present invention as a means for solving the above-mentioned problems is an electrochromic device having two electrodes, an electrochromic layer disposed between the electrodes, and an electrolyte layer existing between the two electrodes. A chromic display element, wherein the electrochromic layer has an electrochromic layer that is a porous structure made of an electrochromic compound that develops color by an oxidation reaction.

  According to the present invention, it is possible to provide an electrochromic display element that can be driven at a low voltage and has a good display quality that does not cause deterioration coloring even when driven repeatedly.

FIG. 1 is a schematic view showing an example of the structure of the electrochromic display element of the present invention. FIG. 2 is a schematic view showing an example of the structure of the electrochromic display element of the present invention. FIG. 3 is a schematic diagram showing an example of the information device of the present invention. FIG. 4 is a schematic view showing an example of the electrochromic light control lens of the present invention. FIG. 5 is a schematic view showing an example of eyeglasses using the electrochromic light control lens of the present invention.

(Electrochromic display element)
The electrochromic display element of the present invention is
An electrochromic display element having two electrodes, an electrochromic layer disposed between the electrodes, and an electrolyte layer existing between the two electrodes,
The electrochromic layer includes an electrochromic layer that is a porous structure made of an electrochromic compound that develops color by an oxidation reaction.
Examples of the electrochromic display element of the present invention include the following first embodiment and second embodiment.

The electrochromic display element of the present invention is, in the first embodiment,
A display board;
Display electrodes provided on the display substrate;
An electrochromic layer provided in contact with the display electrode;
A counter substrate provided facing the display substrate;
A counter electrode provided on a side of the counter substrate facing the display substrate;
A deterioration preventing layer provided in contact with the counter electrode;
An electrolyte layer provided between the display electrode and the counter electrode;
Have
The electrochromic layer is a porous structure made of an electrochromic compound that develops color by an oxidation reaction.
A white reflective layer may be provided between the electrochromic layer and the deterioration preventing layer, and other members may be provided as necessary.

The electrochromic display element of the present invention is, in the second embodiment,
A display board;
Display electrodes provided on the display substrate;
A first electrochromic layer provided in contact with the display electrode;
A counter substrate provided facing the display substrate;
A counter electrode provided on a side of the counter substrate facing the display substrate;
A second electrochromic layer provided in contact with the counter electrode;
An electrolyte layer provided between the display electrode and the counter electrode;
And, if necessary, other members.
The first electrochromic layer is a porous structure made of an electrochromic compound that develops color by an oxidation reaction,
The second electrochromic layer includes an electrochromic compound that develops color by a reduction reaction.

When the electrochromic display element in the prior art is deteriorated in one or a plurality of elements constituting the electrochromic display element due to the repeated driving of color generation and decoloration, coloring with a yellowish brown color is generated as a result. In some cases, the original transparency of the decolored state is lost, and the display quality as an electrochromic display element is impaired. The inventors obtained the knowledge that the degree of deterioration depends on the magnitude of the load applied to the electrochromic display element by driving, and the higher the applied voltage, the easier it is to deteriorate, and based on this knowledge, the present invention The electrochromic display element was found.
By making the electrochromic layer a porous structure made of an electrochromic compound that develops a color by an oxidation reaction, ions serving as charge carriers can easily move, and in addition, a layer that develops a color by an oxidation reaction and ions Increases contact area. In the case where the electrochromic layer has a structure in which ions easily move, the color is easily developed and decolored. As an electrochromic layer in which ions easily move, there is one in which an electrochromic compound is attached to the entire surface of a porous structure made of a substance other than an electrochromic compound. By forming a porous structure with the electrochromic compound itself Simple structure and excellent characteristics.

According to the electrochromic display elements according to the first and second embodiments, it is possible to provide an electrochromic display element having good display quality that does not cause deterioration coloring even when it is repeatedly driven.
The electrochromic display element according to the first and second embodiments can be a transmissive display element and a reflective display element. In the transmissive display element, display characteristics with excellent transparency can be obtained, and reflection can be achieved. In the type display element, bright and clear display characteristics can be obtained.

[Electrochromic Display Element of First Embodiment]
The electrochromic display element according to the first embodiment will be described with reference to the drawings.
FIG. 1 is a schematic diagram illustrating an example of the electrochromic display element 20 according to the first embodiment.
As shown in FIG. 1, the electrochromic display element 20 includes a display substrate 1 and a display electrode 3, a counter substrate 2 and a counter electrode 4 provided to face each other with a space therebetween, and both electrodes ( An electrolyte layer 5 is provided between the display electrode and the counter electrode).
The display electrode 3 has a porous electrochromic layer made of an electrochromic compound that develops color by an oxidation reaction. The electrochromic compound that develops color by the oxidation reaction is preferably a radically polymerizable compound having a triarylamine structure from the viewpoint of high driving durability and light durability.
On the surface of the display electrode 3, it is preferable that an electrochromic layer 6 having a porous structure which is a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine structure is formed.
In the electrochromic display element 20, the electrochromic layer 6 is colored on the surface of the display electrode 3 by an oxidation-reduction reaction. A deterioration preventing layer 7 is formed on the counter electrode 4.
When the electrochromic display element is a reflective display element, a white reflective layer is provided.
In the electrochromic display element 20 shown in FIG. 1, the white reflective layer 8 is provided in contact with the deterioration preventing layer 7. The white reflective layer 8 may be formed in contact with the electrochromic layer 6.
Further, when the electrochromic display element is a transmissive display element, the white reflective layer 8 may not be provided.
In the present invention, a case having a white reflective layer is sometimes referred to as a reflective display element, and a case in which no white reflective layer is formed is sometimes referred to as a transmissive display element.
Although the white reflective layer 8 is illustrated in FIG. 1, even if the white reflective layer 8 is not provided, it is included in the present invention.

<Display board>
The display substrate 1 is a substrate for supporting the display electrode 3 and the electrochromic layer 6.
The material of the display substrate 1 is preferably a light-transmitting material, and examples thereof include glass and plastic films.

<Display electrode>
The display electrode 3 causes the electrochromic layer 6 to develop or decolor by a voltage generated between the electrode and the counter electrode 4. Since the color development in the electrochromic layer 6 is determined by the magnitude of these voltages generated between the display electrode 3 and the counter electrode 4, the color gradation of each electrochromic layer changes depending on the voltage.
The material of the display electrode 3 is preferably a light-transmitting conductive material. Examples thereof include inorganic materials such as indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), and tin oxide doped with antimony (hereinafter referred to as ATO). Among these, InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO are particularly preferable.

<Counter substrate>
The counter substrate 2 is a substrate for supporting the counter electrode and the deterioration preventing layer 7.
The material of the counter substrate 2 is preferably a light-transmitting material, and examples thereof include glass and plastic films.

<Counter electrode>
The counter electrode 4 causes the electrochromic layer 6 to develop or decolor based on the voltage generated between the counter electrode 4 and the display electrode 3.
The material of the counter electrode 4 is not particularly limited as long as it is a conductive material. When a transmissive display element is configured, examples of the light-transmitting conductive material include ITO, FTO, and zinc oxide. Etc. In the case of constituting a reflective element, examples of the conductive metal material include zinc, platinum, and carbon.

<Electrochromic layer>
The electrochromic layer 6 is a porous structure made of an electrochromic compound that develops color by an oxidation reaction. The porous structure composed of the electrochromic compound means that the porous structure is formed of an electrochromic compound, and includes cases where the porous structure includes other components.
The electrochromic layer 6 preferably contains a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine structure from the viewpoint of higher driving durability and light durability. The electrochromic composition preferably contains a radical polymerizable compound other than the radical polymerizable compound having a triarylamine structure and a filler, more preferably contains a polymerization initiator, and further if necessary. And other components.

-Radical polymerizable compound having triarylamine structure-
The radical polymerizable compound having the triarylamine structure is important for imparting an electrochromic function having a redox reaction on the surface of the display electrode 3.
Examples of the radical polymerizable compound having a triarylamine structure include compounds represented by the following general formula 1.

[General Formula 1]
An-Bm
However, n is 1 or 2, m is 0 when n = 2, and m is 0 or 1 when n = 1. At least one of A and B has a radical polymerizable functional group. The A is a structure represented by the following general formula 2, and is bonded to the B at any position from R ₁ to R ₁₅ . The B has a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .

ただし、前記一般式２及び３中、Ｒ₁からＲ₂₁は、いずれも一価の有機基であり、それぞれ同一であっても異なっていてもよく、前記一価の有機基のうち少なくとも１つはラジカル重合性官能基である。

However, in the general formulas 2 and 3, each of R ₁ to R ₂₁ is a monovalent organic group, which may be the same or different, and is at least one of the monovalent organic groups. Is a radically polymerizable functional group.

-Monovalent organic group-
The monovalent organic group in the general formula 2 and the general formula 3 may each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a substituent. An alkoxycarbonyl group, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, an amide group, a substituent; Optionally having a monoalkylaminocarbonyl group, optionally having a dialkylaminocarbonyl group, optionally having a monoarylaminocarbonyl group, optionally having a substituent. Diarylaminocarbonyl group, sulfonic acid group, alkoxysulfonyl group which may have a substituent, aryl which may have a substituent Xylsulfonyl group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, sulfonamide group, optionally substituted monoalkylaminosulfonyl group, substituted A dialkylaminosulfonyl group which may have a group, a monoarylaminosulfonyl group which may have a substituent, a diarylaminosulfonyl group which may have a substituent, an amino group and a substituent A monoalkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryl which may have a substituent Oxy group which may have a substituent alkylthio group which may have a substituent arylthio group, and a heterocyclic group which may have a substituent.
Among these, an alkyl group, an alkoxy group, a hydrogen atom, an aryl group, an aryloxy group, a halogen atom, an alkenyl group, and an alkynyl group are particularly preferable from the viewpoint of stable operation and light durability.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
Examples of the heterocyclic group include carbazole, dibenzofuran, dibenzothiophene, oxadiazole, thiadiazole, and the like.
Examples of the substituent further substituted with the substituent include an alkyl group such as a halogen atom, a nitro group, a cyano group, a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, and an aryloxy group such as a phenoxy group. Group, aryl group such as phenyl group and naphthyl group, and aralkyl group such as benzyl and phenethyl group.

-Radically polymerizable functional group-
The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization.
Examples of the radical polymerizable functional group include a 1-substituted ethylene functional group and a 1,1-substituted ethylene functional group shown below.

ただし、前記一般式（ｉ）中、Ｘ₁は、置換基を有してもよいアリーレン基、置換基を有してもよいアルケニレン基、−ＣＯ−基、−ＣＯＯ−基、−ＣＯＮ（Ｒ₁₀₀）−基〔Ｒ₁₀₀は、水素、アルキル基、アラルキル基、アリール基を表す。〕、又は−Ｓ−基を表す。
前記一般式（ｉ）のアリーレン基としては、例えば、置換基を有してもよいフェニレン基、ナフチレン基などが挙げられる。
前記アルケニレン基としては、例えば、エテニレン基、プロペニレン基、ブテニレン基などが挙げられる。
前記アルキル基としては、例えば、メチル基、エチル基などが挙げられる。
前記アラルキル基としては、例えば、ベンジル基、ナフチルメチル基、フェネチル基などが挙げられる。
前記アリール基としては、例えば、フェニル基、ナフチル基などが挙げられる。
前記一般式（ｉ）で表されるラジカル重合性官能基の具体例としては、ビニル基、スチリル基、２−メチル−１，３−ブタジエニル基、ビニルカルボニル基、アクリロイル基、アクリロイルオキシ基、アクリロイルアミド基、ビニルチオエーテル基などが挙げられる。 (1) As 1-substituted ethylene functional group, the functional group represented by the following general formula (i) is mentioned, for example.

However, in said general formula (i), X < ₁ > is the arylene group which may have a substituent, the alkenylene group which may have a substituent, -CO- group, -COO- group, -CON (R ₁₀₀ ) -group [R ₁₀₀ represents hydrogen, an alkyl group, an aralkyl group or an aryl group. Or -S- group.
Examples of the arylene group of the general formula (i) include a phenylene group and a naphthylene group which may have a substituent.
Examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group.
Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Specific examples of the radical polymerizable functional group represented by the general formula (i) include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyl group, an acryloyloxy group, and an acryloyl group. Examples include amide groups and vinyl thioether groups.

ただし、前記一般式（ii）中、Ｙは、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、ハロゲン原子、シアノ基、ニトロ基、アルコキシ基、−ＣＯＯＲ₁₀₁基〔Ｒ₁₀₁は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、又はＣＯＮＲ₁₀₂Ｒ₁₀₃（Ｒ₁₀₂及びＲ₁₀₃は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、又は置換基を有してもよいアリール基を表し、互いに同一又は異なっていてもよい。）〕を表す。また、Ｘ₂は、前記一般式（ｉ）のＸ₁と同一の置換基及び単結合、アルキレン基を表す。ただし、Ｙ及びＸ₂の少なくともいずれか一方がオキシカルボニル基、シアノ基、アルケニレン基、芳香族環である。
前記一般式（ii）のアリール基としては、例えば、フェニル基、ナフチル基などが挙げられる。
前記アルキル基としては、例えば、メチル基、エチル基などが挙げられる。
前記アルコキシ基としては、例えば、メトキシ基、エトキシ基などが挙げられる。
前記アラルキル基としては、例えば、ベンジル基、ナフチルメチル基、フェネチル基などが挙げられる。
前記一般式（ii）で表されるラジカル重合性官能基の具体例としては、α−塩化アクリロイルオキシ基、メタクリロイル基、メタクリロイルオキシ基、α−シアノエチレン基、α−シアノアクリロイルオキシ基、α−シアノフェニレン基、メタクリロイルアミノ基などが挙げられる。
なお、これらＸ₁、Ｘ₂、Ｙについての置換基に更に置換される置換基としては、例えば、ハロゲン原子、ニトロ基、シアノ基、メチル基、エチル基等のアルキル基、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基等のアリールオキシ基、フェニル基、ナフチル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基などが挙げられる。
前記ラジカル重合性官能基の中でも、アクリロイルオキシ基、メタクリロイルオキシ基が特に好ましい。 (2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following general formula (ii).

However, in the general formula (ii), Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, cyano. Group, nitro group, alkoxy group, —COOR ₁₀₁ group [R ₁₀₁ may have a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. An aryl group, or CONR ₁₀₂ R ₁₀₃ (R ₁₀₂ and R ₁₀₃ may have a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Represents an aryl group and may be the same or different from each other. X ₂ represents the same substituent, single bond, and alkylene group as X _{1 in the} general formula (i). However, at least one of Y and X ₂ is an oxycarbonyl group, a cyano group, an alkenylene group, or an aromatic ring.
Examples of the aryl group of the general formula (ii) include a phenyl group and a naphthyl group.
Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.
Specific examples of the radical polymerizable functional group represented by the general formula (ii) include an α-acryloyl chloride group, a methacryloyl group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α- A cyanophenylene group, a methacryloylamino group, etc. are mentioned.
Examples of the substituent further substituted on the substituents for X ₁ , X ₂ and Y include, for example, a halogen atom, a nitro group, a cyano group, a methyl group, an alkyl group such as an ethyl group, a methoxy group, and an ethoxy group. And aryloxy groups such as a phenoxy group, aryl groups such as a phenyl group and a naphthyl group, and aralkyl groups such as a benzyl group and a phenethyl group.
Among the radical polymerizable functional groups, an acryloyloxy group and a methacryloyloxy group are particularly preferable.

  Preferred examples of the radically polymerizable compound having a triarylamine structure include compounds represented by the following general formulas (1-1) to (1-3).

In the general formulas (1-1) to (1-3), R ₂₇ to R ₈₉ are all monovalent organic groups, which may be the same or different from each other. At least one of the groups is a radically polymerizable functional group.
Examples of the monovalent organic group and the radical polymerizable functional group include the same as those in the general formula (1).

  Examples of the compounds represented by the general formula (1) and the general formulas (1-1) to (1-3) include those shown below. The radical polymerizable compound having the triarylamine structure is not limited thereto.

-Other radical polymerizable compounds-
Unlike the radical polymerizable compound having a triarylamine structure, the other radical polymerizable compound is a compound having at least one radical polymerizable functional group.
Examples of the other radical polymerizable compound include a monofunctional radical polymerizable compound, a bifunctional radical polymerizable compound, a trifunctional or higher functional radical polymerizable compound, a functional monomer, and a radical polymerizable oligomer. Among these, a bifunctional or higher radical polymerizable compound is particularly preferable.
The radical polymerizable functional group in the other radical polymerizable compound is the same as the radical polymerizable functional group in the radical polymerizable compound having the triarylamine structure, and among these, an acryloyloxy group and a methacryloyloxy group are included. Particularly preferred.
Examples of the monofunctional radically polymerizable compound include 2- (2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2 -Ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol Acrylate, phenoxytetraethylene group Call acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the bifunctional radically polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the tri- or higher functional radical polymerizable compound include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, and caprolactone-modified trimethylolpropane. Triacrylate, HPA modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol triacrylate, EO modified glycerol triacrylate, PO modified glycerol triacrylate, Tris (acryloxy) Ethyl) isocyanurate, dipentaerythritol hex Acrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate ( DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.
In the above, EO modification refers to ethyleneoxy modification, and PO modification refers to propyleneoxy modification.

Examples of the functional monomer include those substituted with fluorine atoms such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, and the like. No.-60503, JP-B-6-45770, acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl poly having 20 to 70 siloxane repeating units Examples thereof include vinyl monomers having a polysiloxane group such as dimethylsiloxane diethyl, acrylates and methacrylates. These may be used individually by 1 type and may use 2 or more types together.
Examples of the radical polymerizable oligomers include epoxy acrylate oligomers, urethane acrylate oligomers, and polyester acrylate oligomers.

At least one of the radical polymerizable compound having the triarylamine structure and the other radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure has two or more radical polymerizable functional groups. It is preferable from the point which forms a crosslinked material.
The content of the radical polymerizable compound having a triarylamine structure is preferably 10% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 90% by mass or less with respect to the total amount of the electrochromic compound.
When the content is 10% by mass or more, the electrochromic function of the electrochromic layer can be sufficiently exhibited, the durability is good by repeated use with applied voltage, and the color development sensitivity is good.
Even when the content is 100% by mass, an electrochromic function is possible. In this case, the color development sensitivity to the thickness is the highest. On the other hand, the compatibility with the ionic liquid that is necessary for the transfer of charges may be low, so that there is a possibility that deterioration of electrical characteristics due to a decrease in durability may occur due to repeated use due to applied voltage. The required electrical characteristics differ depending on the process used, so it cannot be said unconditionally. However, when considering the balance between both the color development sensitivity and the repeated durability, the content is more preferably 30% by mass or more and 90% by mass or less.

-Polymerization initiator-
The electrochromic composition efficiently proceeds a crosslinking reaction between the radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. It is preferable to contain a polymerization initiator as necessary.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferable from the viewpoint of polymerization efficiency.
The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-Butylcumyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide Peroxide initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azo initiators such as 4,4′-azobis-4-cyanovaleric acid, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy -Cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- ( acetophenone-based or ketal-based photopolymerization initiators such as o-ethoxycarbonyl) oxime; benzoin, benzoin methyl ester Benzoin ether photopolymerization initiators such as tereline, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyl Benzophenone photopolymerization initiators such as phenyl ether, acrylated benzophenone, 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Examples include thioxanthone photopolymerization initiators such as dichlorothioxanthone.

Examples of other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis (2,4,6-trimethylbenzoyl). Phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compounds, triazine compounds, imidazole compounds, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
In addition, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like.
The content of the polymerization initiator is preferably 0.5 parts by mass or more and 40 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable compound.

-Filler-
There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, an organic filler, an inorganic filler, etc. are mentioned.
Examples of the inorganic filler include metal powders such as copper, tin, aluminum, and indium; silicon oxide (silica), tin oxide, zinc oxide, titanium oxide, aluminum oxide (alumina), zirconium oxide, indium oxide, antimony oxide, Examples thereof include metal oxides such as bismuth oxide, calcium oxide, antimony-doped tin oxide (ATO) and tin-doped indium oxide, and metal fluorides such as tin fluoride, calcium fluoride, and aluminum fluoride. These may be used individually by 1 type and may use 2 or more types together. Among these, metal oxides are preferable from the viewpoint of transparency, stability, and surface treatment, and tin oxide doped with silica, alumina, and antimony (ATO) is particularly preferable.
Examples of the organic filler include resins such as polyester, polyether, polysulfide, polyolefin, silicone, and polytetrafluoroethylene, low molecular compounds such as fatty acids, and pigments such as phthalocyanine. These may be used individually by 1 type and may use 2 or more types together. Among these, a resin is preferable from the viewpoint of transparency and insolubility.

The average primary particle size of the filler is preferably 1 μm or less, and more preferably 10 nm or more and 1 μm or less. When the average primary particle size of the filler is 1 μm or less, there are no coarse particles, the surface state of the resulting film is good, and the surface smoothness is excellent.
The content of the filler is preferably 0.3 parts by mass or more and 1.5 parts by mass or less, more preferably 0.6 parts by mass or more and 0.9 parts by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable compound. preferable.
When the content is 0.3 parts by mass or more, the filler addition effect is sufficiently obtained, the film forming property is good, and when it is 1.5 parts by mass or less, the ratio of the triarylamine compound is appropriate. Thus, good electrochemical characteristics of the produced electrochromic display element can be obtained.
The average thickness of the electrochromic layer is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.4 μm or more and 10 μm or less.

As a method for forming the porous electrochromic layer, there is an extraction method (after the particles made of other substances are mixed and dispersed in the constituent material of the electrochromic layer to form the electrochromic layer, and then the constituent material of the electrochromic layer Is not dissolved, and the particles are dissolved and removed using a solvent that dissolves only the particles to obtain a porous structure). In addition, after forming an electrochromic layer, a foaming method in which foaming is performed by heating, degassing, etc., and after forming an electrochromic layer, a radiation irradiation method in which various radiations are radiated to form pores, etc. May be used, but the extraction method is preferred.
In the extraction method, a porous structure having a desired pore size (void size) can be obtained by selecting the particle size of particles made of other substances added to the constituent material of the electrochromic layer. By using very fine particles having a particle size of, for example, submicron, a porous structure having a pore size of submicron corresponding to the size can be obtained. The particle size of the other substance needs to be smaller than the thickness of the electrochromic layer. As described above, the average thickness of the electrochromic layer is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.4 μm or more and 10 μm or less. Accordingly, since the pore diameter of the porous structure is determined depending on the particle diameter of the particles made of the other substance as described above, it is generally 30 μm or less, but the contact area between the layer that develops color by the oxidation reaction and the ions is reduced. In order to ensure sufficient, the average value of the pore diameter of the porous structure is preferably 5 μm or less.
As a method for obtaining the pore size, a method of measuring the pore size (void size) by SEM observation of a cross section of the electrochromic layer having the porous structure and image processing or the like, A method for analyzing the adsorption behavior of nitrogen gas and the like can be mentioned, but the latter has many restrictions on sample pretreatment and analysis, and the former is preferable.
In the present invention, the diameter of a circle (equivalent circle diameter) equal to the projected area of the pores obtained from the SEM observation image is defined as the pore diameter, and the number average is obtained to obtain the average value of the pore diameters.

As the particles made of other substances added to the constituent material of the electrochromic layer, particles made of a water-soluble material can be used. In particular, water-soluble polymer particles are preferably used, and as a material for the water-soluble polymer, polyvinyl alcohol, polyester, polyacrylic acid, polyethylene oxide, or the like can be suitably used.
What is necessary is just to set the addition amount (ratio) of the particle | grains which consist of said other substance according to the porosity of the desired porous structure.

The porosity of the formed electrochromic layer having a porous structure can be determined as follows.
(Porosity) = {1− (Substantial amount of electrochromic layer) /
[(Film thickness of electrochromic layer × area) × (specific gravity of constituent materials)]} × 100
The porosity of the porous structure is preferably 10% to 80%. When the porosity is 10% or more, the permeability of ions serving as charge carriers is good, and when the porosity is 80% or less, the mechanical strength of the electrochromic layer having the porous structure can be secured, and a display element can be realized.

  As a solvent used for dissolving and removing the water-soluble polymer particles mixed and dispersed in the electrochromic layer, water or an aqueous solvent can be used, and these solvents are heated in the electrochromic layer as necessary. The water-soluble polymer particles dispersed in the electrochromic layer can be dissolved and removed by contacting them for a predetermined time. The method of bringing the solvent into contact with the electrochromic layer is preferably an immersion method, but is not limited thereto, and a method of pouring may be used.

  As described above, there are preferable ranges for the porosity and the pore diameter of the electrochromic layer having the porous structure (porosity: 10% to 80%, average pore diameter: 5 μm or less). If it is within the range, the effect of improving the permeability of the ions as the charge carrier and the effect of sufficiently securing the opportunity of contact between the layer that develops color by the oxidation reaction and the ions act synergistically, The present inventors have found a phenomenon in which the driving voltage of the display element is effectively reduced, the load due to repeated driving or the like is reduced, and deterioration is extremely reduced. The specific range of the both is that the porosity of the electrochromic layer having a porous structure is 60% to 80% and the average value of the pore diameter is 0.5 μm or less.

<Deterioration prevention layer>
The deterioration preventing layer is provided in contact with the counter electrode.
The role of the deterioration preventing layer is to perform a chemical reaction opposite to that of the electrochromic layer and balance the electric charges to suppress corrosion and deterioration of the display electrode and the counter electrode due to an irreversible oxidation-reduction reaction. In addition, the reverse reaction includes acting as a capacitor in addition to the case where the degradation preventing layer is oxidized and reduced.
The material of the deterioration preventing layer is not particularly limited as long as it plays a role of preventing corrosion due to irreversible oxidation-reduction reaction of the display electrode and the counter electrode, and can be appropriately selected according to the purpose. Antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used.
The average thickness of the deterioration preventing layer is preferably from 0.1 μm to 30 μm, and more preferably from 0.4 μm to 10 μm.

<Electrolyte layer>
The electrolyte layer 5 fills a space generated between the counter electrode and the display electrode surrounded by a wall member. The electrolyte layer 5 fills the space so that the electrochromic layer is included in the electrolyte layer. The electrolyte layer 5 moves electric charge between the display electrode and the counter electrode, and promotes color development or decoloration of the electrochromic layer.

As the electrolyte material, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts can be used. Specifically, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaClO ₄ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , KClO ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) ₂ , N (C ₄ H ₉ ) ₄ ClO _{4 and the} like.
An ionic liquid can also be used. As the ionic liquid, any substance that is generally studied and reported can be used. In particular, an organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature.
Examples of molecular structures include cation components such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N-dimethylpyridinium salt, N, Aromatic salts such as pyridinium derivatives such as N-methylpropylpyridinium salts, or aliphatic quaternary ammonium systems such as tetraalkylammonium salts such as trimethylpropylammonium salt, trimethylhexylammonium salt, triethylhexylammonium salt and tetrabutylammonium salt Is mentioned.
As the anion component, a compound containing fluorine is preferable in terms of stability in the atmosphere, and BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ^{− and the} like are also used. ^{_{4 -, B (CN) 4}} - , and the like. An ionic liquid formulated by a combination of these cationic components and anionic components can be used.
Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, and polyethylene. Glycols, alcohols and mixed solvents thereof can be used.

The electrolyte need not be a low-viscosity liquid, and can take various forms such as a gel, a polymer cross-linked type, and a liquid crystal dispersion type. By forming the electrolyte in a gel or solid state, advantages such as improved element strength and improved reliability can be obtained.
As a solidification method, it is preferable to hold the electrolyte and the solvent in the polymer. This is because high ionic conductivity and solid strength can be obtained.
Further, the polymer is preferably a photocurable resin. This is because the device can be manufactured at a low temperature and in a short time as compared with the method of thinning by thermal polymerization or evaporation of the solvent.

  There is no restriction | limiting in particular in the average thickness of the said electrolyte layer, Although it can select suitably according to the objective, 100 nm or more and 10 micrometers or less are preferable.

<White reflective layer>
The white reflective layer is for improving white reflectance in an electrochromic display element.
As a material for the white reflective layer, for example, titanium oxide particles are preferably used, and an aqueous polyurethane resin is preferably used as a binder. The volume average particle size of the titanium oxide particles is preferably 200 nm to 3 μm, and more preferably 250 nm to 2 μm.

<Other members>
There is no restriction | limiting in particular as said other member, According to the objective, it can select suitably, For example, a protective layer, a sealing layer, a hard-coat layer, an antireflection layer etc. are mentioned.

[Electrochromic Display Element of Second Embodiment]
FIG. 2 shows an example of the structure of the electrochromic display element 21 of the second embodiment.
As shown in FIG. 2, the electrochromic display element includes a display substrate 1 and a display electrode 3, a counter substrate 2 and a counter electrode 4 provided to face each other at an interval, and both electrodes (displays). An electrolyte layer 5 is provided between the electrode 3 and the counter electrode 4).
The surface of the display electrode 3 has a first electrochromic layer which is a porous structure made of an electrochromic compound that develops color by an oxidation reaction. The surface of the display electrode 3 has a first electrochromic layer 6 of a porous structure containing a polymer obtained by polymerizing an electrochromic composition containing the radical polymerizable compound having the triarylamine structure of the present invention. It is preferable.
In the electrochromic display element 21, the first electrochromic layer 6 is colored by an oxidation reaction on the surface of the display electrode 3. A second electrochromic layer 9 containing an electrochromic compound that develops color by a reduction reaction is formed on the counter electrode 4. The second electrochromic layer 9 is colored by a reduction reaction on the surface of the counter electrode 4.
Each component of the display substrate, display electrode, counter substrate, counter electrode, electrolyte layer, and first electrochromic layer in the electrochromic display element of the second embodiment is the display of the electrochromic display element of the first embodiment. Since it is almost the same as the substrate, the display electrode, the counter substrate, the counter electrode, the electrolyte layer, and the electrochromic layer, only different components will be described.

<Second electrochromic layer>
The second electrochromic layer 9 preferably supports an electrochromic compound in which the supported particle film develops color by a reduction reaction. Since the supported particle film adsorbs a single molecule of the electrochromic compound, electrons can be efficiently injected into the electrochromic compound using a large surface area. Therefore, the color density at the time of color development of the electrochromic compound can be increased, and the switching speed between color development and decoloration can be increased.

As the support particles constituting the support particle film, conductive fine particles or semiconductive fine particles are preferably used. The conductive fine particles and semiconductive fine particles are not particularly limited and may be appropriately selected depending on the intended purpose, but metal oxides are preferable.
Examples of the metal oxide include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, and oxidation. Examples of the metal oxide include calcium, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, and aluminosilicate. These may be used individually by 1 type and may use 2 or more types together.
Note that when a high response speed is required for color development and decoloration, any of titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide, or a mixture thereof. Is preferably used, and when titanium oxide is used, display with excellent response speed is possible.

The shape of the conductive fine particles and the semiconductive fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a shape having a large surface area (specific surface area) per unit volume. For example, when the conductive fine particles and the semiconductive fine particles are aggregates of nanoparticles, the electrochromic compound can be more efficiently supported because of the large specific surface area.
The electrochromic compound causes an oxidation-reduction reaction by a voltage generated between the display electrode 3 and the counter electrode 4, and develops or decolors (reversible reaction).
The average primary particle diameter of the supported particles is preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm. By setting the average primary particle size to 5 nm or more and 100 nm or less, the second electrochromic layer can be made a transparent layer. As a result, a vivid color is obtained at the time of color development, and a colorless and transparent state is obtained at the time of decoloration.

As the electrochromic compound that develops color by the reduction reaction, either an inorganic electrochromic compound or an organic electrochromic compound may be used.
Examples of the electrochromic compound that develops color by the reduction reaction include, for example, azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styrylspiropyran, and spirooxazine as dye-based and polymer-based electrochromic compounds. , Spirothiopyran, thioindigo, tetrathiafulvalene, terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, Low molecular organic electrochromic compounds such as phthalocyanine, fluoran, fulgide, benzopyran, and metallocene; conductive polymers such as polyaniline and polythiophene Etc., and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, a viologen compound and a dipyridine compound are preferable because a necessary driving voltage can be suppressed to a low level.
There is no restriction | limiting in particular as average thickness of a said 2nd electrochromic layer, Although it can select suitably according to the objective, 500 nm or more and 3 micrometers or less are preferable.

(Method for manufacturing electrochromic display element)
According to a first aspect of the method for manufacturing an electrochromic display element of the present invention, a step of forming a display electrode on a display substrate and an electrochromic layer made of an electrochromic compound that develops color by an oxidation reaction are formed on the display electrode. A step of forming a counter electrode on the side of the counter substrate facing the display substrate, a step of forming a deterioration preventing layer on the counter electrode, and the display electrode and the counter electrode through an electrolyte layer A step of forming the electrochromic layer by applying an electrochromic composition containing water-soluble polymer particles on a display electrode and polymerizing the electrochromic layer after removing the water-soluble polymer particles. Forming a porous structure. Furthermore, other steps can be included as necessary.
In the second embodiment, the method for producing an electrochromic display element according to the present invention includes a step of forming a display electrode on a display substrate, and a first electrochromic compound comprising an electrochromic compound that develops color on the display electrode by an oxidation reaction. Forming a layer, forming a counter electrode on a side of the counter substrate facing the display substrate, and forming a second electrochromic layer containing an electrochromic compound that develops color by a reduction reaction on the counter electrode And the step of pasting the display electrode and the counter electrode through an electrolyte layer, wherein the step of forming the first electrochromic layer comprises displaying an electrochromic composition containing water-soluble polymer particles as a display electrode. A porous structure is formed by removing the water-soluble polymer particles after being applied and polymerized. Comprising the step. Furthermore, other steps can be included as necessary.

<Display electrode formation process>
An ITO film having a film thickness of 50 to 300 nm and a surface resistance of 3 to 200 Ω / □, for example, is formed on the display substrate (for example, a glass substrate having a length of 40 mm and a width of 40 mm) by sputtering. The electrode 3 can be formed.
There is no restriction | limiting in particular as a film-forming method, According to the objective, it can select suitably, For example, other vacuum film-forming methods, such as a sputtering method and an ion plating method, are applicable.

<(First) Electrochromic Layer Formation Step>
The step of forming the electrochromic layer and the first electrochromic layer is performed by applying an electrochromic composition containing water-soluble polymer particles onto a display electrode, polymerizing the electrochromic composition, and then removing the water-soluble polymer particles. Forming a porous structure.
For example, a predetermined amount of water-soluble polymer particles are dispersed on an electrochromic composition containing a radically polymerizable compound having a triarylamine structure on the display electrode, and then a spin coating method, a spray coating method, a bead coating method, a blade coating method. Apply by a suitable printing method. Then, the applied electrochromic composition is crosslinked by applying external energy.
Examples of the external energy include heat, light, and radiation. The heat energy is applied by heating from the coating surface side or the support side using a gas such as air, nitrogen, steam, various heat media, infrared rays, or electromagnetic waves. The heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. or higher and 170 ° C. or lower.
As the energy of the light, a UV irradiation light source such as a high pressure mercury lamp or a metal halide lamp having an emission wavelength mainly in ultraviolet light (UV) can be used, but it is visible according to the absorption wavelength of the radical polymerizable substance or the photopolymerization initiator. A light source can also be selected. Irradiation dose of UV is not particularly limited and may be appropriately selected depending on the intended purpose, 5 mW / cm ² or more 15,000 MW / cm ² or less.
The crosslinked electrochromic composition is immersed in heated water or an aqueous solvent as necessary to dissolve and remove the water-soluble polymer particles dispersed therein.

<White reflective layer forming step>
In the case of producing a reflective display element, a white reflective layer is formed between the electrochromic layer and the deterioration preventing layer.
For example, a 2,2,3,3-tetrafluoropropanol (TFP) dispersion of titanium oxide particles and an aqueous polyurethane resin is applied on the electrochromic layer by a spin coating method. Thereafter, annealing is performed at 120 ° C. for 10 minutes. Thereby, a white reflective layer can be formed.

<Counter electrode formation process>
On the counter substrate (for example, 40 mm long × 40 mm wide glass substrate), for example, an ITO film having a film thickness of 50 to 300 nm and a surface resistance of 3 to 200 Ω / □ is formed by sputtering, and the counter electrode Can be formed.
The film forming method is not limited to the sputtering method, and other vacuum film forming methods such as an ion plating method can be applied.
Next, a deterioration preventing layer or a second electrochromic layer is formed on the counter electrode.

<Deterioration prevention layer forming step>
For example, a dispersion of antimony tin oxide (ATO) is spin-coated on the counter electrode, and an annealing process is performed at 120 ° C. for 10 minutes to form an ATO film.

<Second Electrochromic Layer Formation Step>
First, a carrier particle, for example, a dispersion of titanium oxide is applied on the counter electrode by a spin coating method. Thereafter, an annealing process is performed at 120 ° C. for 15 minutes so that the counter electrode, the supported particles, and the supported particles are partially bonded. This forms a supported particle film.
Thereafter, an electrochromic compound, for example, 4,4 ′-(isoxazole-3,5-diyl) bis (1- (2-phosphoethyl) pyridinium) bromide is contained on the supported particle film in an amount of 2, 2, 3, A 3-tetrafluoropropanol (TFP) solution is applied by spin coating, and an annealing treatment is performed at 120 ° C. for 10 minutes. Thereby, the 2nd electrochromic layer which consists of a titanium oxide particle film and an electrochromic compound can be formed.

<Lamination process>
The laminating step is preferably performed in a glove box substituted with argon gas.
A counter substrate formed with up to the deterioration preventing layer or the second electrochromic layer, a display substrate formed up to the (first) electrochromic layer, or a display substrate formed up to the white reflective layer, a counter electrode and a display electrode Are bonded with the electrolyte layer sandwiched between them.
Specifically, for example, a spherical resin bead having a volume average particle size of 30 μm is sprayed in advance on one side of the display substrate side or the counter substrate side, and then both substrates are bonded together, and the outer periphery is partially bonded, and then bonded. The precursor material of the electrolyte layer is injected into the gap between the combined counter substrate side and display substrate side. Thereafter, ultraviolet light is irradiated for 2 minutes from the display electrode side by a high pressure mercury lamp. Since the precursor material can be photopolymerized and phase-separated by irradiation with ultraviolet light, an electrolyte layer can be formed between both substrates. The ultraviolet light having a center wavelength of 365 nm and an intensity of 50 mW / cm ² can be used.
As an example of a method for preparing the precursor material of the electrolyte layer, first, a propylene carbonate solution of tetrabutylammonium perchlorate (Tetra Butyl Ammonium Perchlorate: TBAP) is used, and a molar concentration of TBAP is about 20 mol / Adjust to L. Thereafter, a mixture of a liquid crystal composition for PNLC (Polymer Network Liquid Crystal), a monomer composition, and a polymerization initiator is mixed into the solution. Thereafter, the molar concentration of TBAP in the propylene carbonate solution is adjusted again to be about 0.04 mol / L. Thereafter, in order to regulate the thickness of the electrolyte layer to be produced, true spherical resin beads having a volume average particle diameter of 30 μm are dispersed in the propylene carbonate solution at a concentration of 0.2% by mass. Thus, it can be set as the precursor material of an electrolyte layer.

(Display device)
The display device of the present invention, the electrochromic display element of the present invention,
A VRAM (first storage means) for storing display data;
And a display controller that controls the electrochromic display element based on the display data, and further includes other means as necessary.

(Information equipment)
The information device of the present invention includes the display device of the present invention and a control device for controlling information displayed on the display device, and further includes other means as necessary.

Hereinafter, the case where the electrochromic display element of the present invention is applied to an electronic book reader will be described.
The electrochromic display element is not limited to an electronic book reader, and can be applied to any information device including a display device such as an electronic advertisement, a mobile personal computer, and a portable terminal.

FIG. 3 shows an example of a schematic structure of the electronic book reader 100.
The electronic book reader 100 includes a display device 101, a main controller 102, a ROM (second storage means) 103, a RAM (third storage means) 104, a flash memory (fourth storage means) 105, a character generator 106, an interface. 107 is included. The display device 101 includes a display panel 111 with a touch panel, a touch panel driver 112, a display controller 113, and a VRAM (first storage means) 114.
In the structure shown in FIG. 3, the character generator 106 is provided outside the display device 101, but the character generator 106 may be provided inside the display device 101. The display panel 111 may not include a touch panel. If there is other input means, the display panel 111 may be provided with other input means. When the display panel 111 does not include a touch panel, the touch panel driver 112 is not necessary.
The arrows shown in FIG. 3 represent typical signals and information flows, and do not represent all the connection relationships of the blocks.

A display panel 111 with a touch panel includes the electrochromic display element and the drive circuit according to the first embodiment. The display panel 111 drives a drive element corresponding to the selected pixel based on the pixel selection signal output from the display controller 113, and applies a predetermined voltage to the selected pixel. The pixel selection signal is a signal that designates the vertical position and the horizontal position of the selected pixel. Further, based on the color designation signal output from the display controller 113, the display panel 111 applies a predetermined voltage to the corresponding display electrode according to the designated color. Based on signals such as a pixel selection signal and a color designation signal, the display panel 111 displays a moving image, a still image, or the like.
The display panel 111 outputs a signal based on the touch position to the touch panel driver 112 when the user touches the touch panel.
Note that since the display panel 111 includes the electrochromic display element 20 of the present invention, the display panel 111 can be driven at a low voltage, and can realize good display quality that does not cause deterioration coloring even when it is repeatedly driven. Actually, even after displaying and erasing a full-color image alternately 1,000 times, no special change was observed in the display state of the image.

Further, the display panel 111 can switch between color development and color erasure at high speed. Actually, the time required from the start of driving to image acquisition and the time required to erase the acquired image were about 500 milliseconds.
In addition, since the display panel 111 has excellent light resistance, the display panel 111 has high fastness to light such as sunlight and room light, and can maintain a highly visible image display even when light is irradiated for a long time.
In fact, even after standing for about 30 minutes after displaying a full-color image, there was no change in the appearance of the image, and blurring of the image could not be recognized.

A VRAM (first storage unit) 114 stores display data for displaying a moving image or a still image on the display panel 111. The display data individually corresponds to a plurality of pixels included in the display panel 111. Therefore, the display data includes display color information corresponding to each pixel.
The display controller 113 reads display data stored in a VRAM (first storage means) 114 at predetermined timings, and displays display colors of a plurality of pixels included in the display panel 111 according to the display data. Control individually. The display controller 113 outputs to the display panel 111 a pixel selection signal for specifying a pixel to be colored and a color designation signal for specifying a color.
The touch panel driver 112 outputs position information corresponding to the position touched by the user on the display panel 111 to the main controller 102.
The main controller 102 includes a RAM (third storage means) 104, a flash memory (fourth storage means) 105, a character generator 106, an interface 107, in accordance with a program stored in a ROM (second storage means) 103. Each unit such as the VRAM (first storage unit) 114 is controlled in an integrated manner.

For example, when the power is turned on by the user, the main controller 102 reads the initial menu screen data from the ROM (second storage means) 103 and refers to the character generator 106 to convert the initial menu screen data into dot data. And the dot data is transferred to a VRAM (first storage means) 114. As a result, the initial menu screen is displayed on the display panel 111. At this time, a list of contents stored in the flash memory 105 is displayed on the display panel 111. When one of the menus on the display panel 111 is selected by the user and the display portion is touched, the main controller 102 acquires the selection content of the user based on the position information from the touch panel driver 112.
When the user designates the content and requests to view the content, the main controller 102 reads the electronic data of the content from the flash memory (fourth storage means) 105, refers to the character generator 106, The electronic data is converted into dot data, and the dot data is transferred to a VRAM (first storage means) 114.
When the user requests to purchase content via the Internet, the main controller 102 connects to a predetermined purchase site via the interface 107 and functions as a normal browser. When the information from the purchase site is displayed on the display panel 111 and the user purchases the content, electronic data of the content is downloaded. The main controller 102 stores the electronic data of the content in the flash memory (fourth storage means) 105.

A ROM (second storage means) 103 stores various programs described in codes readable by the main controller 102 and various data necessary for executing the programs.
A RAM (third storage means) 104 is a working memory.
The flash memory (fourth storage means) 105 stores electronic data of books as contents.
The character generator 106 stores dot data corresponding to various character data.
The interface 107 controls connection with an external device. The interface 107 can connect a memory card, a personal computer, and a public line. The connection to the personal computer and the public line can be either wired or wireless.

  According to the electronic book reader 100, since the electrochromic display element of the present invention is applied to a touch panel, it can be driven at a low voltage, and a good display quality that does not cause deterioration coloring even when repeatedly driven can be obtained. Clear display characteristics can be obtained regardless of whether the display is a reflective display or a transmissive display.

(Electrochromic light control lens)
The electrochromic light control lens of the present invention includes a lens and a thin film light control function unit laminated on the lens, and further includes other members as necessary.
The thin film dimming function unit includes: a first electrode layer stacked on the lens; a first electroactive layer stacked on the first electrode layer; and the first electroactive layer. A laminated insulating porous layer; a porous second electrode layer laminated on the insulating porous layer; and an upper side of the second electrode layer in contact with the second electrode layer; A second electroactive layer formed on one or both of the lower side, a space between the first electrode layer and the second electrode layer, and the first electroactive layer and An electrolyte provided in contact with the second electroactive layer.
One of the first electroactive layer and the second electroactive layer is an electrochromic layer of a porous structure made of an electrochromic compound that develops color by an oxidation reaction, and the other color develops by a deterioration preventing layer or a reduction reaction An electrochromic layer.
The electrochromic light control lens of the present invention has excellent display characteristics that hardly cause deterioration coloring due to repeated driving.

Here, FIG. 4 is a sectional view showing an example of the electrochromic light control lens of the present invention.
Referring to FIG. 4, the electrochromic light control lens 110 includes a lens 120 and a thin film light control function unit 130 stacked on the lens 120. The planar shape of the electrochromic light control lens 110 can be, for example, a round shape.
The thin-film light control function unit 130 has a structure in which a first electrode layer 131, an electrochromic layer 132, an insulating porous layer 133, a second electrode layer 134, a deterioration preventing layer 135, and a protective layer 136 are sequentially stacked. It is a part which performs electrochromic layer 132 light emission / discoloration (light control). Note that the protective layer 136 may be formed on the upper surface (the surface opposite to the lens 120) of the deterioration preventing layer 135, and is not necessarily limited to the first electrode layer 131, the electrochromic layer 132, and the insulating porous layer. 133, the second electrode layer 134, and the deterioration prevention layer 135 may not be formed on the respective side surfaces.

In the electrochromic dimming lens 110, a first electrode layer 131 is provided on the lens 120, and an electrochromic layer 132 is provided in contact with the first electrode layer 131. Further, a second electrode layer 134 is provided on the electrochromic layer 132 so as to face the first electrode layer 131 with the insulating porous layer 133 interposed therebetween.
The insulating porous layer 133 is provided to insulate the first electrode layer 131 and the second electrode layer 134, and the insulating porous layer 133 contains insulating metal oxide fine particles. . The insulating porous layer 133 sandwiched between the first electrode layer 131 and the second electrode layer 134 is filled with an electrolyte.
The second electrode layer 134 is a porous electrode layer in which a large number of through holes penetrating in the thickness direction are formed. A deterioration preventing layer 135 is provided outside the second electrode layer 134. The deterioration preventing layer 135 is also porous in which a large number of through holes penetrating in the thickness direction are formed, and is filled with an electrolyte.
In the electrochromic dimming lens 110, by applying a voltage between the first electrode layer 131 and the second electrode layer 134, the electrochromic layer 132 undergoes an oxidation-reduction reaction due to the transfer of electric charges, and the color changes. .

<Method of manufacturing electrochromic light control lens>
The method of manufacturing the electrochromic light control lens used in the present invention includes a step of sequentially laminating the first electrode layer 131 and the electrochromic layer 132 on the lens 120, and an insulating porous layer 133 on the electrochromic layer 132. A step of laminating a second electrode layer 134, which is a porous electrode layer having a through hole formed so as to face the first electrode layer 131, and a through hole is formed on the second electrode layer 134. A step of laminating the porous porous deterioration preventing layer 135, and the insulating porous layer 133 sandwiched between the first electrode layer 131 and the second electrode layer 134, and the deterioration preventing layer 135 and the second electrode layer. And a step of filling the electrolyte from the through holes formed in the deterioration preventing layer 135 and the second electrode layer 134 via 134, and a step of forming the protective layer 136 on the deterioration preventing layer 135. Including the other steps in accordance to.

Here, the respective through holes formed in the deterioration preventing layer 135 and the second electrode layer 134 are injected when the insulating porous layer 133 or the like is filled with an electrolyte in the manufacturing process of the electrochromic light control lens 110. It is a hole.
Thus, in the electrochromic light control lens 110 of the present invention, the deterioration preventing layer 135 and the second electrode are formed on the insulating porous layer 133 and the like sandwiched between the first electrode layer 131 and the second electrode layer 134. It is possible to fill the electrolyte from through holes formed in the layer 134.
Therefore, it is possible to form the low-resistance second electrode layer 134 before filling the electrolyte, and the performance of the electrochromic light control lens 110 can be improved.
Moreover, since the deterioration preventing layer 135 is provided on the second electrode layer 134, an electrochromic light control lens that operates repeatedly and stably can be realized.

Note that since the through hole is formed in the second electrode layer 134, the deterioration preventing layer 135 is in contact with the second electrode layer 134 outside the second electrode layer 134 (outside the two opposing electrode layers). Can be formed. This is because ions can move between the front and back of the second electrode layer through the through-hole formed in the second electrode layer 134. As a result, since it is not necessary to form the deterioration preventing layer 135 below the second electrode layer 134, the deterioration preventing layer 135 is prevented from being damaged by sputtering or the like when forming the second electrode layer 134. it can.
In addition, when the deterioration preventing layer 135 is formed, a process that can form either a homogeneous deterioration preventing layer 135 is formed on the permeable insulating porous layer 133 and the second electrode layer 134. You can choose as appropriate. Alternatively, the deterioration preventing layer 135 may be formed both above and below the second electrode layer 134 as necessary.
In FIG. 4, the electrochromic layer 132 is formed in contact with the first electrode layer 131, and the deterioration preventing layer 135 is formed in contact with the second electrode layer 134. Have a reductive reaction, and when one carries out a reductive reaction, the other carries out an oxidation reaction. Therefore, the position to be formed may be reversed. That is, the deterioration preventing layer 135 may be in contact with the first electrode layer 131 and the electrochromic layer 132 may be formed in contact with the second electrode layer 134.

Alternatively, the electrochromic layer 132 may be formed in contact with the first electrode layer 131, and the deterioration preventing layer may be formed on both the upper and lower sides of the second electrode layer 134 in contact with the second electrode layer 134. Good. Further, the deterioration preventing layer 135 is formed in contact with the first electrode layer 131, and the electrochromic layer 132 is formed in both the upper and lower sides of the second electrode layer 134 in contact with the second electrode layer 134. Also good.
In the present invention, the deterioration preventing layer and the electrochromic layer may be referred to as an electroactive layer. That is, in the electrochromic light control lens 110 according to the present embodiment, the thin film light control function unit 130 includes the first electrode layer 131 stacked on the lens 120 and the first electrode layer 131 stacked on the first electrode layer 131. 1 electroactive layer, an insulating porous layer 133 laminated on the first electroactive layer, a porous second electrode layer 134 laminated on the insulating porous layer 133, A porous second electroactive layer formed on one or both of the upper side and the lower side of the second electrode layer 134 in contact with the second electrode layer 134, and the first electroactive layer And one of the second electroactive layers is an electrochromic layer 132 of a porous structure including an electrochromic compound that develops color by an oxidation reaction, and the other is an electrochromic compound that develops color by a deterioration preventing layer 135 or a reduction reaction Electrochromic layer comprising.
In the electrochromic dimming lens 110 of the present invention, since the protective layer 136 is formed in the coating process after the electrolyte is injected, the thickness can be reduced with respect to the configuration in which the two lenses are bonded, and the weight is also reduced. Can be done at low cost.
The average thickness of the thin-film light control function unit 130 is preferably 2 μm or more and 200 μm or less. When the thickness of the thin-film light control function unit 130 is 200 μm or less, the round lens can be easily processed and the optical characteristics of the lens are not affected. Further, when the thickness of the thin film light control function unit 130 is 2 μm or more, a good light control function can be obtained.

Here, FIG. 5 is a perspective view showing an example of eyeglasses using the electrochromic light control lens of the present invention. Referring to FIG. 5, the electrochromic dimming glasses 150 include an electrochromic dimming lens 151, a spectacle frame 152, a switch 153, and a power source 154. The electrochromic light control lens 151 is obtained by processing the electrochromic light control lens 110 into a desired shape.
The two electrochromic dimming lenses 151 are incorporated in the spectacle frame 152. The eyeglass frame 152 is provided with a switch 153 and a power source 154. The power source 154 is electrically connected to the first electrode layer 131 and the second electrode layer 134 through a switch 153 by wiring. By switching the switch 153, for example, one of a state in which a positive voltage is applied between the first electrode layer 131 and the second electrode layer 134, a state in which a negative voltage is applied, and a state in which no voltage is applied are selected. The state can be selected.

As the switch 153, for example, an arbitrary switch such as a slide switch or a push switch can be used. However, at least the three states are switchable. As the power source 154, for example, an arbitrary DC power source such as a button battery or a solar battery can be used. The power source 154 can apply a voltage of about plus or minus several volts between the first electrode layer 131 and the second electrode layer 134.
For example, by applying a positive voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic light control lenses 151 are colored in a predetermined color. Further, by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic light control lenses 151 are decolored and become transparent.
However, depending on the characteristics of the material used for the electrochromic layer 132, color is developed by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, and the color is erased by applying a positive voltage. However, it may be transparent. Note that once the color is developed, the color continues even if no voltage is applied between the first electrode layer 131 and the second electrode layer 134.
Hereinafter, materials of each component constituting the electrochromic light control lens 110 of the present invention, a film forming method, and the like will be described in detail.

<Lens>
The material of the lens 120 is not particularly limited as long as it functions as a lens for spectacles, and can be appropriately selected according to the purpose. Moreover, the one where expansion | swelling by a heat history is as small as possible is preferable, and a material with a high glass transition point (Tg) and a material with a small linear expansion coefficient are preferable.
Specifically, in addition to glass, any of those described in the technical summary document on the high refractive index glasses lens of the JPO can be used. Episulfide resin, thiourethane resin, methacrylate resin, polycarbonate Resin, urethane resin, etc., and mixtures thereof can be used. Moreover, you may form the primer for improving a hard coat and adhesiveness as needed.
In the present invention, the lens includes a lens whose power (refractive index) is not adjusted (simple glass plate or the like).

<First electrode layer, second electrode layer>
The material of the first electrode layer 131 and the second electrode layer 134 is not particularly limited as long as it is a conductive material, but when used as a light control glass, light transmittance is ensured. Since it is necessary, a transparent conductive material that is transparent and excellent in conductivity is used. Thereby, the transparency of the glass can be obtained and the coloring contrast can be further increased.

Examples of the transparent conductive material include indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), tin oxide doped with antimony (hereinafter referred to as ATO), and the like. Inorganic materials can be used. In particular, one of indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide) and zinc oxide (hereinafter referred to as Zn oxide) formed by vacuum film formation. It is preferable to use an inorganic material including one.
The In oxide, the Sn oxide, and the Zn oxide are materials that can be easily formed by a sputtering method, and that are excellent in transparency and electrical conductivity. Among these, particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ , and ZnO. Furthermore, transparent network electrodes such as silver, gold, carbon nanotube, and metal oxide, and composite layers thereof are also useful. The network electrode is an electrode in which carbon nanotubes or other highly conductive non-permeable materials are formed in a fine network shape to provide transmittance.

The thicknesses of the first electrode layer 131 and the second electrode layer 134 are adjusted so that an electric resistance value necessary for the oxidation-reduction reaction of the electrochromic layer 132 is obtained. When ITO is used as the material of the first electrode layer 131 and the second electrode layer 134, the thickness of each of the first electrode layer 131 and the second electrode layer 134 is preferably 50 nm or more and 500 nm or less. .
As a manufacturing method of each of the first electrode layer 131 and the second electrode layer 134, a vacuum evaporation method, a sputtering method, an ion plating method, or the like can be used. As long as each material of the first electrode layer 131 and the second electrode layer 134 can be formed by coating, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, Roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet Various printing methods such as a printing method can be used.

The second electrode layer 134 has a large number of fine through-holes penetrating in the thickness direction. For example, a fine through hole can be provided in the second electrode layer 134 by the following method. That is, before forming the second electrode layer 134, it is possible to use a method in which a layer having unevenness is formed in advance as a base layer, and the second electrode layer 134 having unevenness is directly used.
Alternatively, a method may be used in which a convex structure such as a micro pillar is formed before the second electrode layer 134 is formed, and the convex structure is removed after the second electrode layer 134 is formed. Further, before forming the second electrode layer 134, a foaming polymer or the like is sprayed, and after the second electrode layer 134 is formed, a process such as heating or degassing is performed to foam. May be. Alternatively, a method may be used in which various radiations are directly emitted to the second electrode layer 134 to form pores.
Further, as a method for forming a fine through hole in the second electrode layer 134, a colloidal lithography method may be used. The colloidal lithography method is as follows. That is, the conductive film that becomes the second electrode layer 134 is formed on the surface on which the fine particles are dispersed using the dispersed fine particles as a mask by a vacuum film-forming method or the like on the lower layer on which the second electrode layer 134 is laminated. Form. Thereafter, patterning is performed by partially removing the conductive film together with the fine particles.

As a method of forming fine through holes in the second electrode layer 134, a general lift-off method using a photoresist, a dry film, or the like may be used in addition to the colloidal lithography method. Specifically, first, a desired photoresist pattern is formed, then a second electrode layer 134 is formed, and then the photoresist pattern is removed to remove unnecessary portions on the photoresist pattern. In this method, fine through holes are formed in the electrode layer 134.
When a fine through hole is formed in the second electrode layer 134 by a general lift-off method, it is used so that the light irradiation area to the object may be small in order to avoid damage to the lower layer due to light irradiation. It is preferable to use a negative type photoresist.
Negative photoresists include, for example, polyvinyl cinnamate, styrylpyridinium formalized polyvinyl alcohol, glycol methacrylate / polyvinyl alcohol / initiator, polyglycidyl methacrylate, halomethylated polystyrene, diazoresin, bisazide / diene rubber, polyhydroxystyrene / Mention may be made of melamine / photoacid generators, methylated melamine resins, methylated urea resins and the like.

Furthermore, it is possible to form fine through holes in the second electrode layer 134 by a processing apparatus using laser light.
The diameter of the fine through hole provided in the second electrode layer 134 is preferably 10 nm or more and 100 μm or less. When the diameter of the through hole is 10 nm (0.01 μm) or more, the permeation of electrolyte ions is improved. In addition, when the diameter of the fine through hole is 100 μm or less, the display performance just above the fine through hole is not a level that can be visually observed (the size of one pixel electrode (one counter electrode) in a normal display). There is no.
The ratio (hole density) of the hole area to the surface area of the second electrode layer 134 of the fine through holes provided in the second electrode layer 134 can be set as appropriate, and is, for example, 0.01% or more and 40% It can be as follows. If the hole density is too high, the surface resistance of the second electrode layer 134 is increased, which causes a problem that chromic defects are generated due to an increase in the area of the area where the second electrode layer 134 is absent. Further, if the hole density is too low, the permeability of the electrolyte ions is deteriorated.

<Electrochromic layer (electrochromic layer that develops color by oxidation reaction)>
The electrochromic layer 132 is an electrochromic layer that develops color by an oxidation reaction. The electrochromic layer of the electrochromic display element of the first embodiment or the first electrochromic display element of the second embodiment. The same mode as the chromic layer can be adopted.

<Insulating porous layer>
The insulating porous layer 133 has a function of isolating the first electrode layer 131 and the second electrode layer 134 so as to be electrically insulated and holding an electrolyte. The material of the insulating porous layer 133 is not particularly limited as long as the material is porous. However, organic materials and inorganic materials having high insulating properties and durability and excellent film forming properties, and composites thereof. It is preferable to use a body.

As a method of forming the insulating porous layer 133, for example, a sintering method (using fine holes or inorganic particles partially fused by adding a binder or the like to use holes generated between the particles) is used. be able to. As a method for forming the insulating porous layer 133, for example, an extraction method (after forming a constituent layer with an organic or inorganic substance soluble in a solvent and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved in a solvent to To obtain holes) or the like.
As a method of forming the insulating porous layer 133, a foaming method in which a high molecular polymer or the like is foamed by heating or degassing, etc., or a phase change in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. Alternatively, a forming method such as a radiation irradiation method in which pores are formed by radiating various types of radiation may be used. Specific examples include a polymer mixed particle film containing metal oxide fine particles (such as SiO ₂ particles and Al ₂ O ₃ particles) and a polymer binder, and a surface of a porous organic film (such as polyurethane resin and polyethylene resin) electrode layer 134. The resistance is greatly lost, causing display defects.
The thickness of the insulating porous layer 133 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 μm or more and 2 μm or less.

The insulating porous layer 133 is preferably used in combination with an inorganic film. This is because when the second electrode layer 134 formed on the surface of the insulating porous layer 133 is formed by sputtering, damage to the organic material of the insulating porous layer 133 or the electrochromic layer 132 as a lower layer is prevented. This is to reduce.
As the inorganic film, it is preferable to use a material containing ZnS in addition to SiO ₂ . ZnS can be deposited at high speed by sputtering without damaging the electrochromic layer 132 or the like. Furthermore, ZnS—SiO ₂ , ZnS—SiC, ZnS—Si, ZnS—Ge, or the like may be used as a material containing ZnS as a main component.
Here, the ZnS content is preferably 50 mol% or more and 90 mol% or less in order to maintain good crystallinity when the insulating layer is formed. Therefore, particularly preferred materials are ZnS—SiO ₂ (8/2 (mass ratio)), ZnS—SiO ₂ (7/3 (mass ratio)), ZnS, ZnS—ZnO—In ₂ O ₃ —Ga ₂ O _3. (60/23/10/7 (mass ratio)). By using the material as described above as the insulating porous layer 133, a good insulating effect can be obtained with a thin film, and a decrease in film strength and film peeling can be prevented.

<Deterioration prevention layer>
The role of the deterioration preventing layer 135 is to perform a chemical reaction opposite to that of the electrochromic layer 132, and to balance the charge, the first electrode layer 131 and the second electrode layer 134 are corroded or deteriorated by an irreversible oxidation-reduction reaction. Is to suppress it. As a result, the repeated stability of the electrochromic dimming lens 110 is improved. In addition, the reverse reaction includes acting as a capacitor in addition to the case where the degradation preventing layer is oxidized and reduced.
The material of the deterioration preventing layer 135 is not particularly limited as long as it is a material that plays a role of preventing corrosion of the first electrode layer 131 and the second electrode layer 134 due to an irreversible oxidation-reduction reaction. As the material of the deterioration preventing layer 135, for example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used. Furthermore, when the coloring of the deterioration preventing layer does not matter, the same material as the electrochromic material can be used.
The deterioration preventing layer 135 can be composed of a porous thin film that does not hinder electrolyte injection. For example, conductive or semiconductive metal oxide fine particles such as antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, etc., binders such as acrylic, alkyd, isocyanate, urethane, epoxy, phenol, etc. By fixing to the second electrode layer 134, a suitable porous thin film satisfying the electrolyte permeability and the function as a deterioration preventing layer can be obtained.
As a material for the deterioration preventing layer 135, a material that maintains a transparent state in accordance with charge exchange may be used. For example, conductive polymers such as polypyrrole, polythiophene, polyaniline, or derivatives thereof, hybrid polymers of metal complexes and organic ligands, radical polymers, and the like can be given. When these are used, it is necessary to adjust the film density so as not to inhibit the injection of the electrolyte, or to form through holes by laser processing or the like.
These materials may be used as the electrochromic layer 132, and the organic electrochromic compound supported on the conductive or semiconductive fine particles described above may be used as the deterioration preventing layer 135.
As the deterioration prevention layer 135, it is preferable to use highly transparent n-type semiconductor oxide fine particles (n-type semiconductor metal oxide). As a specific example, titanium oxide, tin oxide, zinc oxide, or compound particles containing a plurality of them, or a mixture of particles having a primary particle size of 100 nm or less can be used.

In such a form, a particularly preferred electrochromic material is an organic polymer material. The film can be easily formed by a coating process or the like, and the color can be adjusted and controlled by the molecular structure. Examples of these organic polymer materials include poly (3,4-ethylenedioxythiophene) -based materials, bis (terpyridine) s and iron ion complexing polymers, and the like.
As a method for forming the deterioration preventing layer 135, for example, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used.
As long as the material of the deterioration preventing layer 135 can be applied and formed, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating Various printing methods such as a method, a capillary coating method, a spray coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be used.

<Electrochromic layer (electrochromic layer that develops color by reduction reaction)>
In the case of forming the electrochromic layer 135 that develops color by a reduction reaction without forming the deterioration preventing layer, the same mode as that of the second electrochromic layer in the electrochromic display element of the second embodiment can be adopted.

<Electrolyte>
In the electrochromic dimming lens 110 shown in FIG. 4, the electrolyte is the electrolyte solution through the deterioration preventing layer 135 through the fine through-hole formed in the second electrode layer 134 and the first electrode layer 131 and the first electrode layer 131. The insulating porous layer 133 disposed between the two electrode layers 134 is filled. That is, the electrolyte is filled between the first electrode layer 131 and the second electrode layer 134 so as to be in contact with the electrochromic layer 132 and is deteriorated through the through-hole formed in the second electrode layer 134. It is provided in contact with the prevention layer 135.
The electrolyte may have the same mode as the electrolyte material used for the electrolyte layer of the electrochromic display element of the first embodiment.

<Protective layer>
The role of the protective layer 136 is unnecessary for protecting the device from external stress and chemicals in the cleaning process, preventing leakage of electrolyte, and stable operation of the electrochromic display device such as moisture and oxygen in the atmosphere. For example, to prevent the entry of things. At the same time, transparency, surface smoothness, refractive index, heat resistance, and light resistance are required so as not to impair the function as a lens.
The thickness of the protective layer 136 is preferably 1 μm or more and 200 μm or less.
As a material of the protective layer 136, an ultraviolet curable resin or a thermosetting resin can be used. Specifically, an acrylic resin, a urethane resin, an epoxy resin, or the like is preferably used.
There is no restriction | limiting in particular as a formation method of the protective layer 136, According to the objective, it can select suitably, For example, various film-forming methods, such as a spin coat method, a dip coat method, a spray coat method, a casting method, etc. are mentioned. It is done.
In addition to the protective layer 136, the electrochromic light control lens 110 preferably includes a hard coat layer for preventing scratches and an antireflection layer for suppressing reflection as necessary.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

Example 1
<Production of electrochromic display element>
The electrochromic display element of the first embodiment as shown in FIG. 1 was produced as follows.

<Preparation of electrolyte composition>
An electrolyte composition having the following composition was prepared.
IRGACURE 184 (manufactured by BASF Japan Ltd.): 5 parts by mass PEG400DA (manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (manufactured by Merck):
50 parts by mass Further, 0.2 parts by mass of resin bead spacer (Sekisui Chemical Co., Ltd., Micropearl GS-230) having a volume average particle size of 30 μm was added and dispersed for the purpose of controlling the electrolyte layer thickness. Thus, an electrolyte composition was prepared.

<Formation of display electrode>
An ITO film having an average thickness of 100 nm was formed by sputtering on the entire surface of a glass substrate (40 mm × 40 mm) as a display substrate, and the display electrode 3 was produced. The surface resistance of the display electrode 3 was about 200Ω / □.

・ＩＲＧＡＣＵＲＥ１８４（ＢＡＳＦジャパン株式会社製）： ５質量部
・２官能アクリレートを有するポリエチレングリコールジアクリレート
（ＰＥＧ４００ＤＡ、日本化薬株式会社製）： ５０質量部
・メチルエチルケトン： ９００質量部
・ポリビニルアルコール微粒子（平均粒径１．０μｍ）： ２０質量部
得られたエレクトロクロミック組成物を、前記表示電極上にスピンコート法により塗布し、得られた塗布膜を窒素雰囲気下でＵＶ照射装置（ウシオ電機株式会社製、ＳＰＯＴ ＣＵＲＥ）により１０ｍＷ／ｃｍ²で６０秒間照射し、平均厚み５μｍの架橋したエレクトロクロミック層を形成し、６０℃の水に１０分間浸漬させた後、６０℃の水ですすぎ流し、８０℃のオーブンで１０分間乾燥させた。
このエレクトロクロミック層を形成したＩＴＯ形成基板の質量を量って、予め量っておいたＩＴＯ形成基板の質量を差し引いてエレクトロクロミック層の正確な質量を求め、また触針式の膜厚計で膜厚を測定し、前記計算方法で空隙率を求めたところ、約５０％であった。
また基板端部５ｍｍの部分から上記エレクトロクロミック層を採取して断面をＳＥＭ観察し、画像処理により細孔径（空隙サイズ）の平均値を求めたところ、約０．９μｍであった。 <Formation of electrochromic layer that develops color by oxidation reaction>
In order to form an electrochromic layer that develops color by an oxidation reaction on the display electrode, an electrochromic composition having the following composition was prepared.
Triarylamine compound having a monofunctional acrylate (Exemplary Compound 1 represented by the following structural formula): 50 parts by mass

IRGACURE 184 (manufactured by BASF Japan Ltd.): 5 parts by mass Polyethylene glycol diacrylate having a bifunctional acrylate (PEG 400DA, Nippon Kayaku Co., Ltd.): 50 parts by mass Methyl ethyl ketone: 900 parts by mass Polyvinyl alcohol fine particles (average particles) (Diameter 1.0 μm): 20 parts by mass The obtained electrochromic composition was applied onto the display electrode by a spin coating method, and the obtained coating film was subjected to a UV irradiation apparatus (manufactured by Ushio Electric Co., Ltd.) in a nitrogen atmosphere. SPOT CURE) was irradiated at 10 mW / cm ² for 60 seconds to form a cross-linked electrochromic layer having an average thickness of 5 μm, immersed in water at 60 ° C. for 10 minutes, rinsed with 60 ° C. water, Dry in oven for 10 minutes.
Weigh the mass of the ITO-formed substrate on which this electrochromic layer is formed and subtract the mass of the ITO-formed substrate previously measured to obtain the exact mass of the electrochromic layer. When the film thickness was measured and the porosity was determined by the calculation method, it was about 50%.
Further, the electrochromic layer was collected from the 5 mm end portion of the substrate, the cross section was observed with an SEM, and the average value of the pore diameter (void size) was determined by image processing, which was about 0.9 μm.

<Formation of white reflective layer>
On the electrochromic layer, titanium oxide particles (volume average particle size: 300 nm) and a TFP dispersion of an aqueous polyurethane resin were spin-coated, and a white reflective layer was formed by annealing at 120 ° C. for 10 minutes.

<Formation of counter electrode>
An ITO film having an average thickness of 100 nm was formed on the entire surface of a glass substrate (40 mm × 40 mm) as a counter substrate by sputtering to produce a display electrode. The surface resistance of this display electrode was about 200Ω / □.

<Formation of deterioration prevention layer>
On the counter electrode, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., volume average particle size: about 20 nm) is applied as a deterioration preventing layer by spin coating, and annealed at 120 ° C. for 15 minutes. As a result, a nanostructured semiconductor material composed of a titanium oxide particle film having an average thickness of 1.0 μm was formed.

<Lamination>
The following steps were performed in an argon-substituted glove box.
On the formed deterioration preventing layer, 50 μL of the prepared electrolyte composition was supplied, and the display substrate was bonded so that the white reflective layer formed thereon was opposed and the substrate edge was shifted by 5 mm ( The electrolyte composition was cured by irradiating with a UV (wavelength 250 nm) irradiation device (USHIO Corporation, SPOT CURE) at 10 mW / cm ² for 60 seconds to secure a contact portion for driving. Thus, an electrochromic display element was produced.

  Next, the produced electrochromic display element was evaluated for “deterioration coloring by repeated driving” as follows.

<Evaluation method of deterioration coloring by repeated driving>
The L * value at the time of color erasing was measured before and after 10,000 times of color erasing repeated driving, and the difference between them was used as an index of the degree of deterioration coloring.
The L * value is a characteristic value representing the brightness in the CIELAB color system, and is used here as an index of the brightness when the electrochromic display element is decolored and the color density during color development.
The L * value was measured using a self-made device.
* Repetitive driving conditions: (coloring: constant current application: -0.3 mA / cm ² , application time: 1 second), (decoloring: constant current application: 0.3 mA / cm ² , application time: 1 second) alternately And repeatedly applied.
* Reflective measurements were made on transmissive electrochromic display elements with the elements placed in close contact on a standard white plate. The reflection type electrochromic display element was directly measured for reflection.

-Deterioration coloring due to repeated driving-
A current was applied to the obtained electrochromic display element under the above-described driving conditions, and 10,000 times of color development / erasing was repeated. The voltage during color development was 2.0V. The L * value at the time of erasing immediately after the start is 80.8, the L * value at the time of erasing at the end of 10,000 times is 77.4, and the difference between them (an indicator of the degree of deterioration coloring) is 3. .4, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 2)
<Production of electrochromic display element>
In Example 1, a transmissive display element was formed without forming a white reflective layer on the electrochromic layer that developed color by oxidation reaction, and polyvinyl alcohol was formed when the electrochromic layer that developed color by the oxidation reaction was formed. An electrochromic display element was produced in the same manner as in Example 1 except that fine particles having an average particle diameter of 0.7 μm were used. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.6 μm.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.9V.
The L * value at the time of erasing immediately after the start is 80.4, the L * value at the time of erasing at the end of 10,000 times is 76.8, and the difference between them (an indicator of the degree of deterioration coloring) is 3. .6, and even with visual observation, no deterioration coloring was observed.

(Example 3)
<Production of electrochromic display element>
In Example 2, an electrochromic display element was formed in the same manner as in Example 2 except that an electrochromic layer that developed color by a reduction reaction was formed as follows without forming a deterioration preventing layer on the counter electrode. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.6 μm.

-Formation of electrochromic layer that develops color by reduction reaction-
By applying SP210 (manufactured by Showa Titanium Co., Ltd.) as a titanium oxide nanoparticle dispersion liquid on the counter electrode by a spin coating method and performing an annealing treatment at 120 ° C. for 15 minutes, a titanium oxide particle film (average thickness 1.1 μm) ) Was formed. 2,2 containing 2% by mass of “4,4 ′-(isoxazole-3,5-diyl) bis (1- (2-phosphoethyl) pyridinium) bromide”, which is an electrochromic compound, on the titanium oxide particle film , 3,3-tetrafluoropropanol (hereinafter referred to as “TFP”) solution was spin-coated, and an electrochromic layer that developed color by a reduction reaction was formed by annealing at 120 ° C. for 10 minutes.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.9V. The L * value at the time of erasing immediately after the start is 80.3, the L * value at the time of erasing at the end of 10,000 times is 76.8, and the difference between them (an indicator of the degree of deterioration coloring) is 3. It was as small as .5, and almost no deterioration coloring was observed even in actual visual observation.

Example 4
<Production of electrochromic display element>
In Example 3, in the preparation of the electrochromic composition used to form the electrochromic layer that develops color by oxidation reaction, Example 3 is used except that 30 parts by mass of polyvinyl alcohol fine particles (average particle size 0.7 μm) are used. Similarly, an electrochromic display element was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 60%, and the average value of the pore diameter was about 0.6 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.8V. The L * value at the time of erasing immediately after the start is 80.4, the L * value at the time of erasing at the end of 10,000 times is 77.5, and the difference between them (an indicator of the degree of deterioration coloring) is 2. .9, and even when visually observed, almost no deterioration coloring was observed.

(Example 5)
<Production of electrochromic display element>
In Example 4, in the preparation of the electrochromic composition used to form the electrochromic layer that develops color by oxidation reaction, Example 4 is used except that 40 parts by mass of polyvinyl alcohol fine particles (average particle size 0.7 μm) are used. Similarly, an electrochromic display element was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 70%, and the average value of the pore diameter was about 0.6 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.75V. The L * value at the time of erasing immediately after the start is 80.5, the L * value at the time of erasing at the end of 10,000 times is 77.7, and the difference between them (an indicator of the degree of deterioration coloring) is 2. As small as .8, even with actual visual observation, almost no deterioration coloring was observed.

(Example 6)
<Production of electrochromic display element>
Example 5 is the same as Example 5 except that 50 parts by mass of polyvinyl alcohol fine particles (average particle size 0.7 μm) are used in the preparation of an electrochromic composition used to form an electrochromic layer that develops color by an oxidation reaction. Similarly, an electrochromic display element was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average pore diameter was about 0.6 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.7V. The L * value at the time of erasing immediately after the start is 80.9, the L * value at the time of erasing at the end of 10,000 times is 78.2, and the difference between them (an indicator of the degree of deterioration coloring) is 2. .7, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 7)
<Production of electrochromic display element>
In Example 4, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic display element was prepared in the same manner as in Example 4 except that polyvinyl alcohol fine particles having an average particle diameter of 0.6 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 60%, and the average value of the pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.3V. The L * value at the time of erasing immediately after the start is 81.0, the L * value at the time of erasing at the end of 10,000 times is 80.3, and the difference between them (an index of the degree of deterioration coloring) is 0. .7, which was very small, and even when visually observed, almost no deterioration coloring was observed.

(Example 8)
<Production of electrochromic display element>
In Example 5, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic display element was prepared in the same manner as in Example 5 except that polyvinyl alcohol particles having an average particle diameter of 0.6 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 70%, and the average value of the pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.2V. The L * value at the time of erasing immediately after the start is 80.8, the L * value at the time of erasing at the end of 10,000 times is 80.2, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

Example 9
<Production of electrochromic display element>
In Example 6, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic display element was prepared in the same manner as in Example 6 except that polyvinyl alcohol fine particles having an average particle diameter of 0.6 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average value of the pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.2V. The L * value at the time of erasing immediately after the start is 80.7, the L * value at the time of erasing at the end of 10,000 times is 80.1, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 10)
<Production of electrochromic display element>
In Example 7, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic display element was prepared in the same manner as in Example 7 except that polyvinyl alcohol fine particles having an average particle diameter of 0.3 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 60%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.2V. The L * value at the time of erasing immediately after the start is 81.1, the L * value at the time of erasing at the end of 10,000 times is 80.5, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 11)
<Production of electrochromic display element>
In Example 8, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic display element was prepared in the same manner as in Example 8, except that polyvinyl alcohol fine particles having an average particle size of 0.3 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 70%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.1V. The L * value at the time of erasing immediately after the start is 80.3, the L * value at the time of erasing at the end of 10,000 times is 79.8, and the difference between them (an indicator of the degree of deterioration coloring) is 0. It was very small as .5, and almost no deterioration coloring was observed even in actual visual observation.

(Example 12)
<Production of electrochromic display element>
In Example 9, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic display element was prepared in the same manner as in Example 9 except that polyvinyl alcohol fine particles having an average particle size of 0.3 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.1V. The L * value at the time of erasing immediately after the start is 80.6, the L * value at the time of erasing at the end of 10,000 times is 80.1, and the difference between them (an indicator of the degree of deterioration coloring) is 0. It was very small as .5, and almost no deterioration coloring was observed even in actual visual observation.

(Example 13)
<Production of electrochromic display element>
In Example 3, an electrochromic display element was formed in the same manner as in Example 3 except that polyvinyl alcohol fine particles having an average particle size of 0.6 μm were used when forming an electrochromic layer that developed color by an oxidation reaction. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.8V. The L * value at the time of erasing immediately after the start is 80.4, the L * value at the time of erasing at the end of 10,000 times is 77.7, and the difference between them (an indicator of the degree of deterioration coloring) is 2. .7, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 14)
<Production of electrochromic display element>
In Example 3, an electrochromic display element was formed in the same manner as in Example 3 except that polyvinyl alcohol fine particles having an average particle size of 0.3 μm were used when forming an electrochromic layer that developed color by an oxidation reaction. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.7V. The L * value at the time of erasing immediately after the start is 80.2, the L * value at the time of erasing at the end of 10,000 times is 78.2, and the difference between them (an indicator of the degree of deterioration coloring) is 2. The degradation coloration was hardly seen even when actually observed visually.

・ＩＲＧＡＣＵＲＥ１８４（ＢＡＳＦジャパン株式会社製）： ５質量部
・２官能アクリレートを有するポリエチレングリコールジアクリレート
（ＰＥＧ４００ＤＡ、日本化薬株式会社製）： ５０質量部
・メチルエチルケトン： ９００質量部
得られたエレクトロクロミック組成物を、前記表示電極上にスピンコート法により塗布し、得られた塗布膜を窒素雰囲気下でＵＶ照射装置（ウシオ電機株式会社製、ＳＰＯＴ ＣＵＲＥ）により１０ｍＷ／ｃｍ²で６０秒間照射した。このとき上記酸化反応により発色するエレクトロクロミック層の空隙はほとんど観察されなかった。また計算により求められた空隙率は約５％であった。 (Comparative Example 1)
<Production of electrochromic display element>
In Example 3, an electrochromic display element was produced in the same manner as in Example 3 except that the formation of an electrochromic layer that developed color by an oxidation reaction was performed as follows.
<Formation of electrochromic layer that develops color by oxidation reaction>
In order to form an electrochromic layer that develops color by an oxidation reaction on the display electrode, an electrochromic composition having the following composition was prepared.
Triarylamine compound having a monofunctional acrylate (Exemplary Compound 1 represented by the following structural formula): 50 parts by mass

IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass Polyethylene glycol diacrylate having bifunctional acrylate (PEG400DA, Nippon Kayaku Co., Ltd.): 50 parts by mass Methyl ethyl ketone: 900 parts by mass Obtained electrochromic composition Was applied onto the display electrode by a spin coating method, and the obtained coating film was irradiated at 10 mW / cm ² for 60 seconds with a UV irradiation device (SPOT CURE, manufactured by USHIO INC.) Under a nitrogen atmosphere. At this time, almost no voids in the electrochromic layer that developed color due to the oxidation reaction were observed. The porosity determined by calculation was about 5%.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1, and 10,000 times of color development / erasing repeated driving was performed. The voltage during color development was 2.6V. The L * value at the time of erasing immediately after the start is 80.6, the L * value at the time of erasing at the end of 10,000 times is 51.7, and the difference between them (an indicator of the degree of deterioration coloring) is 28. .9, which was very large, and even with actual visual observation, a remarkable yellowish brown color was observed.

(Example 15)
<Production of electrochromic light control lens>
An electrochromic light control lens as shown in FIG. 4 was produced as follows.

<Formation of first electrode layer and electrochromic layer>
First, a lens having a diameter of 65 mm was prepared, and an ITO film was formed to a thickness of 100 nm by a sputtering method through a metal mask in a 25 mm × 45 mm region and a lead portion to form a first electrode layer 131.
Next, an electrochromic layer that develops color by an oxidation reaction was formed on the ITO film in the same manner as in Example 2. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.6 μm.

<Formation of Insulating Porous Layer, Second Electrode Layer with Fine Through Hole>
Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8% by mass, polyvinyl alcohol 1.2% by mass, water 74% by mass) having an average primary particle diameter of 20 nm is spin-coated on the electrochromic layer 132 and insulated. The porous layer 133 was formed. The film thickness of the formed insulating porous layer 133 was about 2 μm. Furthermore, a fine SiO ₂ fine particle dispersion (silica solid content concentration 1 mass%, 2-propanol 99 mass%) having an average primary particle diameter of 450 nm was spin-coated to form a fine through-hole forming mask (colloidal mask).
Subsequently, an inorganic insulating layer of ZnS—SiO ₂ (8/2 (mass ratio)) was formed to a thickness of 40 nm on the fine through hole forming mask by a sputtering method. Further, an ITO film having a thickness of about 100 nm is formed on the inorganic insulating layer by a sputtering method in a region of 25 mm × 45 mm overlapping with the ITO film formed by the first electrode layer 131 and in a region different from the first electrode layer 131. A second electrode layer 134 was formed using a mask. Note that the ITO film formed in a region different from the first electrode layer 131 is a lead-out portion of the second electrode layer 134.
Thereafter, ultrasonic irradiation was performed in 2-propanol for 3 minutes to remove 450 nm SiO ₂ fine particles as a colloidal mask. It was confirmed by SEM observation that the second electrode layer 134 in which minute through holes of about 250 nm were formed was formed. The sheet resistance of the second electrode layer 134 was about 100Ω / □.

<Formation of deterioration prevention layer>
Subsequently, an antimony tin oxide particle dispersion was applied as a deterioration preventing layer 135 on the second electrode layer 134 by a spin coating method. Then, a nanostructured semiconductor material composed of an antimony tin oxide particle film having an average thickness of 1.0 μm was formed by performing an annealing treatment at 120 ° C. for 15 minutes.

<Electrolyte filling>
Tetrabutylammonium perchlorate as an electrolyte and dimethyl sulfoxide and polyethylene glycol (weight average molecular weight: 200) as a solvent were mixed at a mass ratio of 12:54:60 to obtain an electrolytic solution. Then, the light control lens formed up to the deterioration preventing layer 135 was immersed for 1 minute, and then dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

<Formation of protective layer>
Furthermore, an ultraviolet curable adhesive (SD-17, manufactured by DIC Corporation) was spin-coated, and the protective layer 136 was formed to have an average thickness of about 3 μm by curing by ultraviolet light irradiation. Thereby, the electrochromic light control lens shown in FIG. 4 was obtained.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1, and repeated driving of erasing and decoloring 10,000 times. The voltage during color development was 2.0V. The L * value at the time of erasing immediately after the start is 81.4, the L * value at the time of erasing at the end of 10,000 times is 77.2, and the difference between them (an indicator of the degree of deterioration coloring) is 4. .2 and was hardly deteriorated even when visually observed.

(Example 16)
<Production of electrochromic light control lens>
Example 15 is the same as Example 15 except that 30 parts by mass of polyvinyl alcohol fine particles (average particle size 0.7 μm) are used in the preparation of an electrochromic composition used to form an electrochromic layer that develops color by an oxidation reaction. Similarly, an electrochromic light control lens was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 60%, and the average value of the pore diameter was about 0.6 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 2.0V. The L * value at the time of erasing immediately after the start is 80.9, the L * value at the time of erasing at the end of 10,000 times is 77.8, and the difference between them (an indicator of the degree of deterioration coloring) is 3. .1 and the deterioration coloration was hardly seen even in actual visual observation.

(Example 17)
<Production of electrochromic light control lens>
In Example 16, the preparation of an electrochromic composition used to form an electrochromic layer that develops color by an oxidation reaction was the same as Example 16 except that 40 parts by mass of polyvinyl alcohol fine particles (average particle size 0.7 μm) were used. Thus, an electrochromic light control lens was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 70%, and the average value of the pore diameter was about 0.6 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.9V. The L * value at the time of erasing immediately after the start is 81.0, the L * value at the time of erasing at the end of 10,000 times is 78.0, and the difference between them (an index of the degree of deterioration coloring) is 3. The degradation coloration was hardly seen even when actually observed visually.

(Example 18)
<Production of electrochromic light control lens>
In Example 17, in the preparation of the electrochromic composition used for forming the electrochromic layer that develops color by oxidation reaction, Example 17 is used except that 50 parts by mass of polyvinyl alcohol fine particles (average particle size 0.7 μm) are used. Similarly, an electrochromic light control lens was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average pore diameter was about 0.6 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.85V. The L * value at the time of erasing immediately after the start is 81.4, the L * value at the time of erasing at the end of 10,000 times is 78.4, and the difference between them (an indicator of the degree of deterioration coloring) is 3. The degradation coloration was hardly seen even when actually observed visually.

(Example 19)
<Production of electrochromic light control lens>
In Example 16, an electrochromic light control lens was formed in the same manner as in Example 16 except that when the electrochromic layer that developed color by oxidation reaction was formed, polyvinyl alcohol fine particles having an average particle diameter of 0.6 μm were used. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 60%, and the average value of the pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.4V. The L * value at the time of erasing immediately after the start is 81.5, the L * value at the time of erasing at the end of 10,000 times is 80.7, and the difference between them (an index of the degree of deterioration coloring) is 0. .8, which was very small, and even when visually observed, almost no deterioration coloring was observed.

(Example 20)
<Production of electrochromic light control lens>
In Example 17, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic light control lens is obtained in the same manner as in Example 17 except that polyvinyl alcohol fine particles having an average particle diameter of 0.6 μm are used. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 70%, and the average value of the pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.3V. The L * value at the time of erasing immediately after the start is 81.3, the L * value at the time of erasing at the end of 10,000 times is 80.6, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .7, which was very small, and even when visually observed, almost no deterioration coloring was observed.

(Example 21)
<Production of electrochromic light control lens>
In Example 18, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic light control lens is obtained in the same manner as in Example 18 except that polyvinyl alcohol fine particles having an average particle diameter of 0.6 μm are used. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average value of the pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.3V. The L * value at the time of erasing immediately after the start is 81.2, the L * value at the time of erasing at the end of 10,000 times is 80.5, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .7, which was very small, and even when visually observed, almost no deterioration coloring was observed.

(Example 22)
<Production of electrochromic light control lens>
In Example 19, an electrochromic light control lens was prepared in the same manner as in Example 19 except that polyvinyl alcohol fine particles having an average particle size of 0.3 μm were used when an electrochromic layer that developed color by an oxidation reaction was formed. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 60%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.3V. The L * value at the time of erasing immediately after the start is 81.6, the L * value at the time of erasing at the end of 10,000 times is 80.9, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .7, which was very small, and even when visually observed, almost no deterioration coloring was observed.

(Example 23)
<Production of electrochromic light control lens>
In Example 20, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic light control lens was prepared in the same manner as in Example 20 except that polyvinyl alcohol fine particles having an average particle diameter of 0.3 μm were used. Produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 70%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.2V. The L * value at the time of erasing immediately after the start is 80.8, the L * value at the time of erasing at the end of 10,000 times is 80.2, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 24)
<Production of electrochromic light control lens>
In Example 21, an electrochromic light control lens was produced in the same manner as in Example 21 except that polyvinyl alcohol fine particles having an average particle size of 0.3 μm were used when forming an electrochromic layer that developed color by an oxidation reaction. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.2V. The L * value at the time of erasing immediately after the start is 81.1, the L * value at the time of erasing at the end of 10,000 times is 80.5, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .6, which was very small, and even with actual visual observation, almost no deterioration coloring was observed.

(Example 25)
<Production of electrochromic light control lens>
In Example 15, an electrochromic light control lens was produced in the same manner as in Example 15 except that polyvinyl alcohol fine particles having an average particle diameter of 0.6 μm were used when forming an electrochromic layer that developed color by an oxidation reaction. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.5 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 2.0V. The L * value at the time of erasing immediately after the start is 81.2, the L * value at the time of erasing at the end of 10,000 times is 78.4, and the difference between them (an indicator of the degree of deterioration coloring) is 2. As small as .8, even with actual visual observation, almost no deterioration coloring was observed.

(Example 26)
<Production of electrochromic light control lens>
In Example 15, when forming an electrochromic layer that develops color by an oxidation reaction, an electrochromic light control lens is obtained in the same manner as in Example 15 except that polyvinyl alcohol fine particles having an average particle diameter of 0.3 μm are used. Was made. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 55%, and the average pore diameter was about 0.2 μm.
<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage at the time of color development was 1.9V. The L * value at the time of erasing immediately after the start is 81.0, the L * value at the time of erasing at the end of 10,000 times is 78.9, and the difference between them (an indicator of the degree of deterioration coloring) is 2. .1 and the deterioration coloration was hardly seen even in actual visual observation.

(Example 27)
<Production of electrochromic light control lens>
In Example 24, an electrochromic tone layer was formed in the same manner as in Example 24 except that an electrochromic layer that developed color by a reduction reaction was formed as follows without forming a deterioration preventing layer on the second electrode. An optical lens was produced. At this time, the porosity of the electrochromic layer that developed color by the oxidation reaction was about 80%, and the average pore diameter was about 0.2 μm.

-Formation of electrochromic layer that develops color by reduction reaction-
On the second electrode, SP210 (manufactured by Showa Titanium Co., Ltd.) as a titanium oxide nanoparticle dispersion is applied by spin coating, and annealed at 120 ° C. for 15 minutes to obtain a titanium oxide particle film (average thickness 1). .1 μm) was formed. 2,2 containing 2% by mass of “4,4 ′-(isoxazole-3,5-diyl) bis (1- (2-phosphoethyl) pyridinium) bromide”, which is an electrochromic compound, on the titanium oxide particle film , 3,3-tetrafluoropropanol (hereinafter referred to as “TFP”) solution was spin-coated, and an electrochromic layer that developed color by a reduction reaction was formed by annealing at 120 ° C. for 10 minutes.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic light control lens under the same driving conditions as in Example 1 and repeated driving of erasing / erasing 10,000 times. The voltage during color development was 1.2V. The L * value at the time of erasing immediately after the start is 81.3, the L * value at the time of erasing at the end of 10,000 times is 80.6, and the difference between them (an indicator of the degree of deterioration coloring) is 0. .7, which was very small, and even when visually observed, almost no deterioration coloring was observed.

(Comparative Example 2)
<Production of electrochromic light control lens>
In Example 15, an electrochromic light control lens was produced in the same manner as in Example 15 except that the formation of the electrochromic layer that developed color by the oxidation reaction was performed in the same manner as in Comparative Example 1. At this time, almost no voids in the electrochromic layer that developed color due to the oxidation reaction were observed. The porosity determined by calculation was about 5%.

<Evaluation>
-Deterioration coloring due to repeated driving-
A current was applied to the produced electrochromic display element under the same driving conditions as in Example 1, and 10,000 times of color development / erasing repeated driving was performed. The voltage at the time of color development was 2.9V. The L * value at the time of erasing immediately after the start is 81.1, the L * value at the time of erasing at the end of 10,000 times is 53.3, and the difference between them (an indicator of the degree of deterioration coloring) is 27. .8, which was very large, and even with actual visual observation, a remarkable yellowish brown color was observed.

DESCRIPTION OF SYMBOLS 1 Display substrate 2 Counter substrate 3 Display electrode 4 Counter electrode 5 Electrolyte layer 6 Electrochromic layer (1st electrochromic layer)
7 Deterioration Prevention Layer 8 White Reflective Layer 9 Second Electrochromic Layer 20 Electrochromic Display Element 21 Electrochromic Display Element 100 Information Equipment (Electronic Book Reader)
101 Display device 102 Control device (main controller)
103 ROM (second storage means)
104 RAM (third storage means)
105 Flash memory (fourth storage means)
106 Character Generator 107 Interface 110 Electrochromic Dimming Lens 111 Display Panel with Touch Panel 112 Touch Panel Driver 113 Display Controller 114 VRAM (First Storage Unit)
DESCRIPTION OF SYMBOLS 120 Lens 130 Thin film light control function part 131 1st electrode layer 132 Electrochromic layer 133 Insulating porous layer 134 2nd electrode layer 135 Deterioration prevention layer 136 Protective layer 150 Electrochromic light control glasses 151 Electrochromic light control lens 152 Eyeglass frame 153 Switch 154 Power supply

JP 2003-121883 A JP 2006-106669 A JP 2010-33016 A JP 2012-137736 A JP 2015-14743 A

Claims (14)

  An electrochromic display element having two electrodes, an electrochromic layer disposed between the electrodes, and an electrolyte layer existing between the two electrodes, wherein the electrochromic layer has an electrochromic color generated by an oxidation reaction. An electrochromic display element having an electrochromic layer which is a porous structure made of a chromic compound.   A display substrate; a display electrode provided on the display substrate; an electrochromic layer provided in contact with the display electrode; a counter substrate provided opposite to the display substrate; and a display on the counter substrate A counter electrode provided on the side facing the substrate, a deterioration preventing layer provided in contact with the counter electrode, and an electrolyte layer provided between the display electrode and the counter electrode, An electrochromic display element, wherein the electrochromic layer is a porous structure made of an electrochromic compound that develops color by an oxidation reaction.   The electrochromic display element according to claim 2, further comprising a white reflective layer between the electrochromic layer and the deterioration preventing layer.   The electrochromic display element according to claim 2, wherein the electrochromic layer includes a polymer obtained by polymerizing an electrochromic composition including a radical polymerizable compound having a triarylamine structure.   A display substrate; a display electrode provided on the display substrate; a first electrochromic layer provided in contact with the display electrode; a counter substrate provided to face the display substrate; A counter electrode provided on the side of the substrate facing the display substrate, a second electrochromic layer provided in contact with the counter electrode, and an electrolyte layer provided between the display electrode and the counter electrode And the first electrochromic layer is a porous structure made of an electrochromic compound that develops color by an oxidation reaction, and the second electrochromic layer contains an electrochromic compound that develops color by a reduction reaction Including electrochromic display element.   The electrochromic display element according to claim 5, wherein the first electrochromic layer includes a polymer obtained by polymerizing an electrochromic composition including a radical polymerizable compound having a triarylamine structure.   The porosity of the porous structure made of an electrochromic compound that develops color by the oxidation reaction is 60% to 80%, and the average value of the pore diameters is 0.5 μm or less. Electrochromic display element.   8. A method of manufacturing an electrochromic display element according to claim 2, wherein a step of forming a display electrode on a display substrate, and an electrochromic compound that develops color on the display electrode by an oxidation reaction A step of forming an electrochromic layer, a step of forming a counter electrode on the side of the counter substrate facing the display substrate, a step of forming a deterioration preventing layer on the counter electrode, the display electrode and the counter electrode And the step of forming the electrochromic layer comprises applying an electrochromic composition containing water-soluble polymer particles on a display electrode and polymerizing the water-soluble polymer. A method for producing an electrochromic display element, comprising a step of forming a porous structure by removing polymer particles.   8. A method of manufacturing an electrochromic display element according to claim 5, wherein a step of forming a display electrode on a display substrate and an electrochromic compound that develops color on the display electrode by an oxidation reaction. A step of forming one electrochromic layer, a step of forming a counter electrode on the side of the counter substrate facing the display substrate, and a second electrochromic layer containing an electrochromic compound that develops color by a reduction reaction on the counter electrode And the step of bonding the display electrode and the counter electrode via an electrolyte layer, wherein the step of forming the first electrochromic layer comprises an electrochromic composition containing water-soluble polymer particles Porous material by removing the water-soluble polymer particles after the product is applied on the display electrode and polymerized Method of manufacturing an electrochromic display device comprising the step of forming the granulated material.   A display device comprising: the electrochromic display element according to claim 1; a VRAM that stores display data; and a display controller that controls the electrochromic display element based on the display data.   An information device comprising: the display device according to claim 10; and a control device that controls information to be displayed on the display device. A lens, and a thin-film light control function unit laminated on the lens,
The thin film dimming function unit includes a first electrode layer stacked on the lens, a first electroactive layer stacked on the first electrode layer, and the first electroactive layer. A laminated insulating porous layer; a porous second electrode layer laminated on the insulating porous layer; and an upper side of the second electrode layer in contact with the second electrode layer; A second electroactive layer formed on one or both of the lower side, a space between the first electrode layer and the second electrode layer, and the first electroactive layer and An electrolyte provided in contact with the second electroactive layer,
One of the first electroactive layer and the second electroactive layer is an electrochromic layer of a porous structure made of an electrochromic compound that develops color by an oxidation reaction, and the other color develops by a deterioration preventing layer or a reduction reaction An electrochromic light control lens that is an electrochromic layer.   The electrochromic layer of the porous structure made of an electrochromic compound that develops color by the oxidation reaction includes a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine structure. Electrochromic light control lens.   The electrochromic according to claim 12 or 13, wherein the porous structure made of an electrochromic compound that develops color by the oxidation reaction has a porosity of 60% to 80% and an average pore diameter of 0.5 µm or less. Photochromic lens.

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